Structural Study of Hydrated/Dehydrated Manganese Thiophene-2,5-diphosphonate Metal Organic Frameworks, Mn 2 (O 3 P?C 4 H 2 S?PO 3 )?2H 2 O

Abstract : Synthesis of thiophene-2,5-diphosphonic acid 2 is reported, and its use for synthesis of the original pristine materials Mn2(O3P–C4H2S–PO3)·2H2O 3 is reported. The structure of material 3 has been fully resolved from single-crystal X-ray diffraction. Mn2(O3P–C4H2S–PO3)·2H2O 3 crystallizes in a monoclinic cell (space group P2) with the following parameters: a = 11.60(1) Å, b = 4.943(5) Å, c = 19.614(13) Å, β = 107.22°. A noticeable feature of the structure of compound 3 is the orientation of the thiophene heterocycles that adopt two different orientations in two successive layers (along c). Thermal analysis of compound 3 indicates that the water molecules are easily removed from 160 to 230 °C while the dehydrated structure is stable up to 500 °C. The dehydrated compound obtained from 3 can be rehydrated to give the polymorphic compound Mn2(O3P–C4H2S–PO3)·2H2O 4, which crystallizes in an orthorhombic cell (space group Pnam) with the following parameters: a = 7.5359(3) Å, b = 7.5524(3) Å, c = 18.3050(9) Å. The main difference between the structures of 3 and 4 arises from both the orientation of the thiophene rings (herringbone-type organization in 4) and the structure of the inorganic layers. The thiophene-2,5-diphosphonic acid moieties engaged in materials 3 and 4 adopt a different orientation likely due to rotation around the P–C bonds and via the dehydrated state 5, which is likely more flexible than the hydrated states. Study of the magnetic properties performed on compound 3 and 4 and on the dehydrated compounds Mn2(O3P–C4H2S–PO3) 5 complemented by the structural study has permitted us to characterize the antiferromagnetic ground state of sample 3, a weak ferromagnetic component in sample 4, and complete paramagnetic behavior in sample 5.
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Inorganic Chemistry, American Chemical Society, 2012, 51 (19), pp.10251 - 10261. 〈http://pubs.acs.org/doi/abs/10.1021/ic301187y〉. 〈10.1021/ic301187y〉
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Soumis le : mercredi 5 juillet 2017 - 16:20:59
Dernière modification le : mercredi 4 juillet 2018 - 01:19:06

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Jean-Michel Rueff, Olivier Perez, Alain Pautrat, Nicolas Barrier, Gary B. Hix, et al.. Structural Study of Hydrated/Dehydrated Manganese Thiophene-2,5-diphosphonate Metal Organic Frameworks, Mn 2 (O 3 P?C 4 H 2 S?PO 3 )?2H 2 O. Inorganic Chemistry, American Chemical Society, 2012, 51 (19), pp.10251 - 10261. 〈http://pubs.acs.org/doi/abs/10.1021/ic301187y〉. 〈10.1021/ic301187y〉. 〈hal-01556896〉

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