Short-Range and long-range magnetic ordering, in third generation brannerite type inorganic-organic vanadates: [{Mn(Bpy)}(VO) ]≈(HO) and [{Mn(Bpy) }(VO)]≈(HO)
Chemistry of Materials, ISSN: 0897-4756, Vol: 22, Issue: 19, Page: 5543-5553
2010
- 26Citations
- 12Captures
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Article Description
The three-dimensional [{Mn(Bpy)}(VO)]≈(H O) and [{Mn(Bpy)}(VO) ]≈(HO) inorganic-organic compounds, where Bpy is 4,4′-bipyridine, (CHN), have been synthesized using mild hydrothermal conditions under autogenous pressure at 170 °C during three days, obtaining single-crystals suitable for X-ray structure determination. The compounds crystallize in the monoclinic system, space group C2/m, with a = 16.706(5), b = 3.5265(4), c = 11.558(5) Å, and β = 100.77(5)° for 1, and a = 16.305(6), b = 3.5304(11), c = 17.788(6) Å, and β = 116.87(4)° for 2. Single crystal X-ray diffraction reveals that both crystal structures are composed of inorganic layers pillared by organic ligands. However, 1 possesses simple layers, while 2 is constructed from double inorganic sheets. This structural organization gives rise to channels along the [010] direction, in which the crystallization water molecules are located. The thermogravimetry and thermodiffractometry experiments show that both crystal structures have a dynamical and reversible response to the removal and uptake of crystallization water molecules. Magnetic, ESR, specific heat, and neutron measurements indicate that both phases possess one-dimensional ferromagnetic coupling of the Mn(II) ions above the Néel temperature. Below 4 K for 1 and 7.5 K for 2, a three-dimensional antiferromagnetic order is established. The sigmoidal shape of the magnetization curves indicates that the three-dimensional antiferromagnetic order can be reverted by the application of higher magnetic fields. © 2010 American Chemical Society.
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