Vibrational spectra of four alkaline earth cyclo-hexaphosphates

Abstract

FT-IR and FT-Raman spectra of four alkaline earth (Mg, Ca, Sr and Ba) cyclo-hexaphosphates have been recorded and analysed. FT-Raman spectra of the deuterated analogues of these compounds are used to clear the ambiguity regarding the OH vibrations in the low frequency region. The spectra reveal that the P 6O 18 6− anion ring in all compounds have independent PO 4 tetrahedra present in it. The P-O(P)and P-O(M′)(M′-Mg, Ca, Sr and Ba) bonds become stronger as the cation size decreases. The P 6O 18 6− anion ring is distorted in the Mg and Ca compounds. In the Sr and Ba compounds, free and hydrogen bonded water molecules of varying strength are present, whereas in Mg and Ca compounds no free water molecules exist. The POP bridge angle of the Mg, Ca and Sr compounds are estimated using the correlations between the POP bridge stretching frequencies and the bridge angle value.