The aim of the present work is to highlight the unique role of anilato-ligands, derivatives of the 2,5-dioxy-1,4-benzoquinone framework containing various substituents at the 3 and 6 positions (X = H, Cl, Br, I, CN, etc.), in engineering a great variety of new materials showing peculiar magnetic and/or conducting properties. Homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of such materials, spanning from graphene-related layered magnetic materials to intercalated supramolecular arrays, ferromagnetic 3D monometallic lanthanoid assemblies, multifunctional materials with coexistence of magnetic/conducting properties and/or chirality and multifunctional metal-organic frameworks (MOFs) will be discussed herein. The influence of (i) the electronic nature of the X substituents and (ii) intermolecular interactions i.e., H-Bonding, Halogen-Bonding, π-π stacking and dipolar interactions, on the physical properties of the resulting material will be also highlighted. A combined structural/physical properties analysis will be reported to provide an effective tool for designing novel anilate-based supramolecular architectures showing improved and/or novel physical properties. The role of the molecular approach in this context is pointed out as well, since it enables the chemical design of the molecular building blocks being suitable for self-assembly to form supramolecular structures with the desired interactions and physical properties.

The mixed-valence Fe^IIFe^III 2D coordination polymer formulated as [TAG][Fe^IIFe^III(ClCNAn)₃]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn^2– = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [Fe^IIFe^III(ClCNAn)₃]⁻ establish in the ab plane, with an intralayer metal–metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe–O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C₃ symmetry to the structure and engages in intermolecular N–H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10^–3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type Fe^IIFe^III 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.

Here we report on new tris(haloanilato)metallate(iii) complexes with general formula [M(X₂An)₃]³⁻, their crystal structures, DFT calculations and magnetic properties.

Tuning of luminescent and SIM properties is herein reported, in a novel flexible 3D anilato-based Er ^III -MOF, displaying reversible shrinkage/expansion from a distorted hexagonal to a 3,6-brickwall rectangular structure.