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Issue 2, 2015
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Influence of the synthesis route on the formation of 12R/10H-polytypes and their magnetic properties within the Ba(Ce,Mn)O3 family

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Abstract

The influence of the Mn precursor on the formation of polytypes was studied within the Ba–Ce–Mn–O system. Minor changes in the mean oxidation state of Mn cations guide the reaction route through different pathways to obtain the iso-stoichiometric 12R-Ba4CeMn4O12−δ or 10H-Ba5Ce1.25Mn3.75O15−δ compounds. This behaviour was controlled using MnO2 or MnCO3 as starting chemical precursors. The understanding of such tendencies allowed the synthesis of the new 10H-Ba5Ce0.83Mn4.17O15−δ composition through a two-step reaction route. This compound crystallizes in a hexagonal symmetry with space group P63/mmc (No. 194) and cell parameters a = b = 5.77650(6) Å and c = 23.8590(4) Å. Its main characteristic is the presence of pure [Mn4O15] oligomers, establishing a difference with respect to the already known 10H-Ba5Ce1.25Mn3.75O15 polytype for which the principal feature was a mixed metal occupancy within [Ce0.25Mn3.75O15] tetramers. This difference generates strong antiferromagnetic (AFM) exchanges, contrary to the metamagnetic-like transition observed in 10H-Ba5Ce1.25Mn3.75O15. It is concluded that full Mn occupancy in [Mn3O12] or [Mn4O15] sub-units induces a robust AFM character.

Graphical abstract: Influence of the synthesis route on the formation of 12R/10H-polytypes and their magnetic properties within the Ba(Ce,Mn)O3 family

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Publication details

The article was received on 17 May 2014, accepted on 29 Jul 2014 and first published on 31 Jul 2014


Article type: Paper
DOI: 10.1039/C4NJ00798K
Citation: New J. Chem., 2015,39, 829-835
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    Influence of the synthesis route on the formation of 12R/10H-polytypes and their magnetic properties within the Ba(Ce,Mn)O3 family

    M. A. Macías, O. Mentré, C. Pirovano, P. Roussel, S. Colis and G. H. Gauthier, New J. Chem., 2015, 39, 829
    DOI: 10.1039/C4NJ00798K

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