Use this identifier to quote or link this document: http://hdl.handle.net/2072/374601

Title:	Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks
Author:	Sahadevan, Suchithra Ashoka; Abherve, Alexandre; Monni, Noemi; Saenz de Pipaon, Cristina; Galan-Mascaros, José Ramoń; Waerenborgh, Joaõ C.; Vieira, Bruno J. C.; Auban-Senzier, Pascale; Pillet; Bendeif, El-Eulmi; Alemany, Pere; Canadell, Enric; Mercuri, Maria Laura; Avarvari, Narcis
Abstract:	The mixed-valence FeIIFeIII 2D coordination poly- mer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2− = chlorocyanoanilate dia- nionic 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.
Publication date:	2018-09-10
Subject(s):	54
Rights:	L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/
Pages:	12611 p.
Document type:	Article Article - Accepted version
DOI:	10.1021/jacs.8b08032
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