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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 Anions Lligands Electric conductivity Anions Ligands |
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: https://doi.org/10.1021/jacs.8b08032 |
It is part of: | Journal of the American Chemical Society, 2018, vol. 140, num. 39, p. 12611-12621 |
URI: | http://hdl.handle.net/2445/184290 |
Related resource: | https://doi.org/10.1021/jacs.8b08032 |
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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