NDLI: $A_{x}(H_{3}O)_{2−x}Mn_{5}(HPO_{3})_{6}$ (A = Li, Na, K and $NH_{4}):$ open-framework manganese(II) phosphites templated by mixed cationic species

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Arriortua, María I. Orive, Joseba Fernández, Jesús Rodríguez Lezama, Luis Fernández De Luis, Roberto
Description	Author Affiliation: Orive J ( Departamento de Ciencia de los Materiales, FCFM, Universidad de Chile, Av. Beauchef 851, Santiago 8370448, Chile. joseba.orive@ing.uchile.cl.); Fernández de Luis R ( Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo. 48940 Leioa, Spain. roberto.fernandez@ehu.eus maribel.arriortua@ehu.es and Basque Center for Materials, Applications & Nanostructures (BC Materials) Parque Tecnológico de Zamud); Fernández JR ( CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander, Spain. rodrigufj@unican.es.); Lezama L ( Basque Center for Materials, Applications & Nanostructures (BC Materials) Parque Tecnológico de Zamudio, Camino de Ibaizabal, Edificio 500 - 1°, 48160 Derio, Spain. roberto.fernandez@bcmaterials.net maribel.arriortua@ehu.es and Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología); Arriortua MI ( Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo. 48940 Leioa, Spain. roberto.fernandez@ehu.eus maribel.arriortua@ehu.es and Basque Center for Materials, Applications & Nanostructures (BC Materials) Parque Tecnológico de Zamud)
Abstract	$A_{x}(H_{3}O)_{2−x}Mn_{5}(HPO_{3})_{6}$ (A = Li, x = 0.55 (1-Li); A = Na, x = 0.72 (2-Na); A = K, x = 0.30 (3-K); A = $NH_{4},$ x = 0.59 $(4-NH_{4}))$ phases were synthesized by employing mild hydrothermal conditions. 1-Li was studied by single crystal X-ray diffraction, while sodium, potassium and ammonium containing analogues were obtained as polycrystalline samples and characterized by powder X-ray diffraction. The four compounds were characterized by ICP-Q-MS, thermal analysis and XPS, IR, UV/Vis and EPR spectroscopy. Single crystal data indicate that 1-Li crystallizes in the Pc1 space group with lattice parameters a = 10.3764(1) Å and c = 9.4017(1) Å with Z = 2. The crystal structure of these phases is constituted by a three-dimensional $[Mn(II)_{5}(HPO_{3})_{6}]^{2−}$ anionic skeleton templated by alkali metal and ammonium cations together with protonated water molecules. Such an inorganic framework is formed by layers of edge-sharing $MnO_{6}$ octahedra placed in the ab plane and joined along the c direction through phosphite pseudotetrahedra. The sheets display 12-membered ring channels parallel to the c-axis, ca. 5 Å in diameter, where the extraframework species display a strong disorder. EPR measurements point to the existence of short range ferromagnetic interactions around 12 K. Magnetic susceptibility and heat capacity measurements show that all the compounds exhibit long range antiferromagnetic order below circa 4 K, with a significant magnetocaloric effect around the Neel temperature.
ISSN	14779226
Issue Number	30
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-07-26
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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