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Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO 2)(OH)2 and Mn4(CO2(CH 2)nCO2)3(OH)2

Saines, P.J., Jain, P., Cheetham, A.K. (2011) Evolution of the structures and magnetic properties of the manganese dicarboxylates, Mn2(CO2(CH2)nCO 2)(OH)2 and Mn4(CO2(CH 2)nCO2)3(OH)2. Chemical Science, 2 (10). pp. 1929-1939. ISSN 20416520 (ISSN). (doi:10.1039/c1sc00253h) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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Abstract

Two new series of basic Mn dicarboxylate frameworks, Mn2(CO 2(CH2)nCO2)(OH)2 (where n = 0, 2, 4 and 5) and Mn4(CO2(CH2) nCO2)3(OH)2 (where n = 3 and 5), have been synthesised and the evolution of their structures with changing length of the dicarboxylate ligand was examined. Compounds in the Mn 2(CO2(CH2)nCO2)(OH) 2 series contain 2 dimensionally inorganically connected layers, which are bridged in the third dimension by the dicarboxylate ligand. While the compounds in this series with n = 0 or 2 contain only octahedrally coordinated Mn, the frameworks with longer ligands, n = 4 or 5, have a 1:1 ratio of octahedrally and trigonal bipyramidally coordinated cations. Structures in the Mn4(CO2(CH2)nCO2) 3(OH)2 series contain inorganically connected double chains of MnOx polyhedra, which comprise an equal number of octahedra and trigonal bipyramids. Trigonal bipyramidal coordination environments are very rarely found in dicarboxylate frameworks and the roles of the longer dicarboxylate ligands and the d5 electronic configuration of Mn 2+ in their formation are discussed. The magnetic properties of Mn2(CO2(CH2)2CO2)(OH) 2 have also been examined. It undergoes two magnetic transitions. The higher temperature transition to a two dimensionally ordered antiferromagnetic phase occurs around 44 K, in low applied fields, and is followed by a transition to a three dimensionally ordered canted antiferromagnetic state near 36 K. The Néel temperature of this phase is unusually high for a transition metal dicarboxylate and the factors thought to support this are examined. © The Royal Society of Chemistry 2011.

Item Type: Article
DOI/Identification number: 10.1039/c1sc00253h
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - Chem. Sci. [Field not mapped to EPrints] AD - Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ, United Kingdom [Field not mapped to EPrints] AD - Department of Chemistry and Biochemistr, Florida State University, Tallahassee, FL 32306, United States [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Uncontrolled keywords: Antiferromagnetic phase, Antiferromagnetic state, Applied field, Coordination environment, Dicarboxylates, Double chain, Electronic configuration, Higher temperatures, Magnetic transitions, New series, Octahedrally coordinated, Trigonal bipyramids, Antiferromagnetic materials, Antiferromagnetism, Carboxylation, Ligands, Magnetic properties, Manganese, Manganese oxide, Transition metals, Carbon dioxide
Subjects: Q Science > QC Physics > QC173.45 Condensed Matter
Q Science > QD Chemistry > QD478 Solid State Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Paul Saines
Date Deposited: 07 Oct 2015 10:06 UTC
Last Modified: 29 May 2019 16:04 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/50728 (The current URI for this page, for reference purposes)
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