期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 39, 页码 12611-12621出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b08032
关键词
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资金
- CNRS
- Erasmus program
- RFI Regional project LUMOMAT (project ASCO MMM)
- PIA project Lorraine Universite d'Excellence [ANR-15-IDEX-04-LUE]
- Fondazione di Sardegna-Convenzione triennale tra la Fondazione di Sardegna e gli Atenei Sardi, Regione Sardegna-L.R. 7/2007 annualita [2016-DGR 28/21]
- INSTM
- Spanish Ministerio de Economia y Competitividad [FIS2012-37549-C05-05, FIS2015-64886-C5-4-P, CTQ2015-64579-C3-3-P, CTQ2015-71287-R]
- Generalitat de Catalunya [2014SGR301, 2017SGR797]
- Generalitat de Catalunya (XRQTC)
- Generalitat de Catalunya (CERCA program)
- Spanish MINECO through the Severo Ochoa Centers of Excellence Program [SEV-2015-0496]
- Fundacao para a Ciencia e a Tecnologia (FCT, Portugal) [UID/Multi/04349/2013]
- University of Angers
The mixed-valence (FeFeIII)-Fe-II 2D coordination polymer formulated as [TAG][(FeFeIII)-Fe-II(CICNAn)(3)]center dot(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn(2-) = 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 [(FeFeIII)-Fe-II(ClCNAn)(3)](-) establish in the ab plane, with an intralayer metal-metal distance of 7.860 angstrom, 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 C-3 symmetry to the structure and engages in intermolecular N-H center dot center dot center dot 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. Mossbauer 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 x 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 (FeFeIII)-Fe-II 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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