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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
Abhervé, Alexandre
Monni, Noemi
Sáenz de Pipaón, Cristina
Galan-Mascaros, José Ramón
Waerenborgh, João C.
Vieira, Bruno J. C.
Auban-Senzier, Pascale
Pillet, Sébastien
Bendeif, El-Eulmi
Alemany i Cahner, Pere
Canadell, Enric, 1950-
Mercuri, Maria Laura
Avarvari, Narcis
Keywords: Conductivitat elèctrica
Electric conductivity
Issue Date: 10-Sep-2018
Publisher: American Chemical Society
Abstract: The 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.
Note: Versió postprint del document publicat a:
It is part of: Journal of the American Chemical Society, 2018, vol. 140, num. 39, p. 12611-12621
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ISSN: 0002-7863
Appears in Collections:Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))
Articles publicats en revistes (Ciència dels Materials i Química Física)

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