Synthesis and structural characterization of two new polyoxometalate-based organic/inorganic charge-transfer hybrids 4(2,2-DPA)·pseudo-alpha -H4SiMo12O40·4DMF·2H2O and 4(2, 2-DPA)·pseudo-alpha -H4SiMo12O40·2H2O (2, 2-DPA=2, 2-dipyridylamine)

This work reports the thermal dehydration of the oxocarbonic salt Li2C5O5·2H2O studied by IR and Raman spectroscopy, by ex situ and in situ techniques. The loss of the crystallization water is not only reflected by the disappearing of the pertinent bands, but also by the change in the crystalline phase, as evidenced by the alteration in the splitting pattern of the oxocarbon modes and by differential scanning calorimetry. In the anhydrous salt spectra, a great number of overtones and combination bands appear in the 2000–4000 cm-1 region, indicating an increased anharmonicity. The enhanced splitting suggests that the anhydrous phase belongs to a less symmetric unit cell. The tetrahedral environment around the lithium ion is preserved, as suggested by the shifts of some modes in the 300–600 cm-1 region on isotopic substitution from 7Li to 6Li. Raman and thermoanalytical data seem to indicate that the crystallization water is released in a single-step process.