title: 2D and 3D Anilato-Based Heterometallic M(I)M(III) Lattices: The Missing Link.
abstract: The similar bis-bidentate coordination mode of oxalato and anilato-based ligands is exploited here to create the first examples of 2D and 3D heterometallic lattices based on anilato ligands combining M(I) and a M(III) ions, phases already observed with oxalato but unknown with anilato-type ligands. These lattices are prepared with alkaline metal ions and magnetic chiral tris(anilato)metalate molecular building blocks: [M(III)(C6O4X2)3](3-) (M(III) = Fe and Cr; X = Cl and Br; (C6O4X2)(2-) = dianion of the 3,6-disubstituted derivatives of 2,5-dihydroxy-1,4-benzoquinone, H4C6O4). The new compounds include two very similar 2D lattices formulated as (PBu3Me)2[NaCr(C6O4Br2)3] (1) and (PPh3Et)2[KFe(C6O4Cl2)3](dmf)2 (2), both presenting hexagonal [M(I)M(III)(C6O4X2)3](2-) honeycomb layers with (PBu3Me)(+) in 1 or (PPh3Et)(+) and dmf in 2 inserted between them. Minor modifications in the synthetic conditions yield the novel 3D lattice (NEt3Me)[Na(dmf)][NaFe(C6O4Cl2)3] (3), in which hexagonal layers analogous to 1 and 2 are interconnected through Na(+) cations, and (NBu3Me)2[NaCr(C6O4Br2)3] (4), the first heterometallic 3D lattice based on anilato ligands. This compound presents two interlocked chiral 3D (10,3) lattices with opposite chiralities. Attempts to prepare 4 in larger quantities result in the 2D polymorph of compound 4 (4'). Magnetic properties of compounds 1, 3, and 4' are reported, and in all cases we observe, as expected, paramagnetic behaviors that can be satisfactorily reproduced with simple monomer models including a zero field splitting (ZFS) of the corresponding S = 3/2 for Cr(III) in 1 and 4' or S = 5/2 for Fe(III) in 3.
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
authors.forename: Samia
authors.initials: S
authors.lastname: Benmansour
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
authors.forename: Cristina
authors.initials: C
authors.lastname: Vallés-García
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
authors.forename: Patricia
authors.initials: P
authors.lastname: Gómez-Claramunt
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
authors.forename: Guillermo
authors.initials: G
authors.lastname: Mínguez Espallargas
authors.affiliation: Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2, 46980 Paterna, Valencia, Spain.
authors.forename: Carlos J
authors.initials: CJ
authors.lastname: Gómez-García