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The intercalation reaction of pyridine with manganese thiophosphate, MnPS3

Joy, Pattayil Alias and Vasudevan, Sukumaran (1992) The intercalation reaction of pyridine with manganese thiophosphate, MnPS3. In: Journal of the American Chemical Society, 114 (20). pp. 7792-7801.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja00046a027

Abstract

The intercalation of pyridine in the layered manganese thiophosphate, MnPS3, has been examined in detail by a variety of techniques. The reaction is interesting since none of the anticipated changes in optical and electrical properties associated with intercalation of electron donating molecules is observed. The only notable change in the properties of the host lattice is in the nature of the low-temperature magnetic ordering; while MnPS3 orders antiferromagnetically below 78 K, the intercalated compound shows weak ferromagnetism probably due to a canted spin structure. Vibrational spectra clearly show that the intercalated species are pyridinium ions solvated by neutral pyridine molecules. The corresponding reduced sites of the host lattice, however, were never observed. The molecules in the solvation shell are exchangeable. Although the reaction appears to be topotactic and reversible, from XRD, a more detailed analysis of the products of deintercalation reveal that it is not so. The intercalation proceeds by an ion exchange/intercalation mechanism wherein the intercalated species are pyridinium ions solvated by neutral molecules with charge neutrality being preserved not by electron transfer but by a loss of Mn2+ ions from the lattice. The experimental evidence leading to this conclusion is discussed and it is shown that this model can account satisfactorily for the observed changes (or lack of it) in the optical, electrical, vibrational, and magnetic properties.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Keywords: Mps3;Absorption;Transport;Chemistry;Complexes;Spectra; Feps3; Nips3;Model;Feocl.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 30 May 2011 05:40
Last Modified: 30 May 2011 05:40
URI: http://eprints.iisc.ernet.in/id/eprint/37773

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