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Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks
- Suchithra Ashoka SahadevanSuchithra Ashoka SahadevanLaboratoire MOLTECH-Anjou UMR 6200, UFR Sciences, CNRS, Université d’Angers, Bât. K, 2 Bd. Lavoisier, 49045 Angers, FranceDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato (Cagliari), ItalyMore by Suchithra Ashoka Sahadevan,
- Alexandre AbhervéAlexandre AbhervéLaboratoire MOLTECH-Anjou UMR 6200, UFR Sciences, CNRS, Université d’Angers, Bât. K, 2 Bd. Lavoisier, 49045 Angers, FranceMore by Alexandre Abhervé,
- Noemi MonniNoemi MonniDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato (Cagliari), ItalyMore by Noemi Monni,
- Cristina Sáenz de PipaónCristina Sáenz de PipaónInstitute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology (BIST), Avenida Països Catalans 16, 43007 Tarragona, SpainMore by Cristina Sáenz de Pipaón,
- José Ramón Galán-MascarósJosé Ramón Galán-MascarósInstitute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology (BIST), Avenida Països Catalans 16, 43007 Tarragona, SpainICREA, Passeig Lluís Companys 23, 08010 Barcelona, SpainMore by José Ramón Galán-Mascarós,
- João C. WaerenborghJoão C. WaerenborghCentro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, 2695-066 Bobadela LRS, PortugalMore by João C. Waerenborgh,
- Bruno J. C. VieiraBruno J. C. VieiraCentro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, 2695-066 Bobadela LRS, PortugalMore by Bruno J. C. Vieira,
- Pascale Auban-SenzierPascale Auban-SenzierLaboratoire de Physique des Solides, UMR 8502, Bât. 510, CNRS-Université Paris-Sud, 91405 Orsay, FranceMore by Pascale Auban-Senzier,
- Sébastien Pillet ,
- El-Eulmi Bendeif ,
- Pere Alemany*Pere Alemany*[email protected]Departament de Ciència de Materials i Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, SpainMore by Pere Alemany,
- Enric Canadell*Enric Canadell*[email protected]Institut de Ciència de Materials de Barcelona (CSIC), Campus de la UAB, E-08193 Bellaterra, SpainMore by Enric Canadell,
- Maria Laura Mercuri*Maria Laura Mercuri*[email protected]Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, I-09042 Monserrato (Cagliari), ItalyMore by Maria Laura Mercuri, and
- Narcis Avarvari*Narcis Avarvari*[email protected]Laboratoire MOLTECH-Anjou UMR 6200, UFR Sciences, CNRS, Université d’Angers, Bât. K, 2 Bd. Lavoisier, 49045 Angers, FranceMore by Narcis Avarvari
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.
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