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Title: Ionothermal synthesis of open-framework metal phosphates with a Kagome lattice network exhibiting canted anti-ferromagnetism

Abstract

Four open-framework transition-metal phosphates; (NH4)2Co3(HPO4)2F4 (1), (NH4)Co3(HPO4)2(H2PO4)F2 (2), KCo3(HPO4)2(H2PO4)F2 (3), and KFe3(HPO4)2(H2PO4)F2 (4); are prepared by ionothermal synthesis using pyridinium hexafluorophosphate as the ionic liquid. Single-crystal X-ray diffraction analyses reveal that the four compounds contain cobalt/iron–oxygen/fluoride layers with Kagomé topology composed of interlinked face-sharing MO3F3/MO4F2 octahedra. PO3OH pseudo-tetrahedral groups augment the [M3O6F4] (1)/[M3O8F2] layers on both sides to give M3(HPO4)2F4 (1) and M3(HPO4)2F2 (2–4) layers. These layers are stacked along the a axis in a sequence AA…, resulting in the formation of a layer structure for (NH4)2Co3(HPO4)2F4(1). In NH4Co3(HPO4)2(H2PO4)F2 and KM3(HPO4)2(H2PO4)F2, the M3(HPO4)2F2 layers are stacked along the a axis in a sequence AAi… and are connected by [PO3(OH)] tetrahedra, giving rise to a 3-D open framework structure with 10-ring channels along the [001] direction. The negative charges of the inorganic framework are balanced by K+/NH4+ ions located within the channels. The magnetic transition metal cations themselves form layers with stair-case Kagomé topology. Magnetic susceptibility and magnetization measurements reveal that all four compounds exhibit a canted anti-ferromagnetic ground state (Tc = 10 or 13 K for Co and Tc = 27 K for Fe) with different canting angles. The full orbital moment is observed for both Co2+ and Fe2+.

Authors:
 [1];  [2];  [3];  [4]
  1. Ruhr-Universitat Bochum
  2. Max Plank Institute for Chemical Physics of Solids, Dresden, Germany
  3. Ruhr Universitat Bochum
  4. Ames Laboratory
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1166703
Report Number(s):
IS-J 8451
Journal ID: ISSN 2050-7526; JMCCCX
DOE Contract Number:  
DE-AC02-07CH11358
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 2; Journal Issue: 35; Journal ID: ISSN 2050-7526
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Guangmei, Valldor, Martin, Mallick, Bert, and Mudring, Anja-Verena. Ionothermal synthesis of open-framework metal phosphates with a Kagome lattice network exhibiting canted anti-ferromagnetism. United States: N. p., 2014. Web. doi:10.1039/c4tc00290c.
Wang, Guangmei, Valldor, Martin, Mallick, Bert, & Mudring, Anja-Verena. Ionothermal synthesis of open-framework metal phosphates with a Kagome lattice network exhibiting canted anti-ferromagnetism. United States. https://doi.org/10.1039/c4tc00290c
Wang, Guangmei, Valldor, Martin, Mallick, Bert, and Mudring, Anja-Verena. 2014. "Ionothermal synthesis of open-framework metal phosphates with a Kagome lattice network exhibiting canted anti-ferromagnetism". United States. https://doi.org/10.1039/c4tc00290c.
@article{osti_1166703,
title = {Ionothermal synthesis of open-framework metal phosphates with a Kagome lattice network exhibiting canted anti-ferromagnetism},
author = {Wang, Guangmei and Valldor, Martin and Mallick, Bert and Mudring, Anja-Verena},
abstractNote = {Four open-framework transition-metal phosphates; (NH4)2Co3(HPO4)2F4 (1), (NH4)Co3(HPO4)2(H2PO4)F2 (2), KCo3(HPO4)2(H2PO4)F2 (3), and KFe3(HPO4)2(H2PO4)F2 (4); are prepared by ionothermal synthesis using pyridinium hexafluorophosphate as the ionic liquid. Single-crystal X-ray diffraction analyses reveal that the four compounds contain cobalt/iron–oxygen/fluoride layers with Kagomé topology composed of interlinked face-sharing MO3F3/MO4F2 octahedra. PO3OH pseudo-tetrahedral groups augment the [M3O6F4] (1)/[M3O8F2] layers on both sides to give M3(HPO4)2F4 (1) and M3(HPO4)2F2 (2–4) layers. These layers are stacked along the a axis in a sequence AA…, resulting in the formation of a layer structure for (NH4)2Co3(HPO4)2F4(1). In NH4Co3(HPO4)2(H2PO4)F2 and KM3(HPO4)2(H2PO4)F2, the M3(HPO4)2F2 layers are stacked along the a axis in a sequence AAi… and are connected by [PO3(OH)] tetrahedra, giving rise to a 3-D open framework structure with 10-ring channels along the [001] direction. The negative charges of the inorganic framework are balanced by K+/NH4+ ions located within the channels. The magnetic transition metal cations themselves form layers with stair-case Kagomé topology. Magnetic susceptibility and magnetization measurements reveal that all four compounds exhibit a canted anti-ferromagnetic ground state (Tc = 10 or 13 K for Co and Tc = 27 K for Fe) with different canting angles. The full orbital moment is observed for both Co2+ and Fe2+.},
doi = {10.1039/c4tc00290c},
url = {https://www.osti.gov/biblio/1166703}, journal = {Journal of Materials Chemistry C},
issn = {2050-7526},
number = 35,
volume = 2,
place = {United States},
year = {Wed Jan 01 00:00:00 EST 2014},
month = {Wed Jan 01 00:00:00 EST 2014}
}