Sahadevan, SuchithraAbhervé, AlexandreMonni, NoemiSáenz de Pipaón, CristinaGalan-Mascaros, José RamónWaerenborgh, João C.Vieira, Bruno J. C.Auban-Senzier, PascalePillet, SébastienBendeif, El-EulmiAlemany i Cahner, PereCanadell, Enric, 1950-Mercuri, Maria LauraAvarvari, Narcis2022-03-222022-03-222018-09-100002-7863https://hdl.handle.net/2445/184290The mixed-valence FeIIFeIII 2D coordination polymer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2− = 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 [FeIIFeIII(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 FeIIFeIII 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.11 p.application/pdfeng(c) American Chemical Society , 2018Conductivitat elèctricaAnionsLligandsElectric conductivityAnionsLigandsinfo:eu-repo/semantics/article6836422022-03-22info:eu-repo/semantics/openAccess