Chemical states and lattice dynamics of alpha-diimine Fe2+ complexes intercalated into gamma-zirconium phosphate

The alpha-diimine Fe2+ complexes, Fe(phen)3]2+, Fe(bpy)3]2+, and Fe(terpy)2]2+, (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridyl, terpy: alpha,alpha',alpha'-tripyridine) were intercalated into zirconium dihydrogenphosphate phosphate dihydrate (gamma-zirconium phosphate, gamma-ZrP), Zr(PO4)(H2PO4).2H2O. The rate of the intercalation, the molar ratio of Fe to Zr, was found to be 3.82-7.76%. M?ssbauer spectra indicated that one part of Fe(phen)3]2+ and Fe(bpy)3]2+ changed from a low-spin Fe2+ to high-spin Fe2+ state on intercalation, but Fe(terpy)2]2+ did not change in chemical state. The lattice dynamics of the complexes and the intercalation compounds were investigated in terms of the temperature dependence of the area intensity on the M?ssbauer spectra. A linear relationship was established for all the complex salts and the intercalation compounds investigated between the lnA(T)/A(82)] and absolute temperature, T, where A(T) and A(82) show the intensities of a doublet at T and 82 K of the M?ssbauer spectra, respectively. From the slope of the linear relation, the theta2M values, which were derived based on the Debye approximation of lattice vibration, were evaluated for the complex salts and the intercalation compounds. The Fe2+ complexes showed theta2M values of 1.27 to 2.32 x 10(6), whereas the intercalation compounds showed very similar values to each other, ranging from 2.19 to 2.39 x 10(6), irrespective of different alpha-diimine ligands. The results were explained in terms of the characteristic layered structure of zirconium phosphate, and by the tight bond between the alpha-diimine Fe2+ complexes and the host gamma-ZrP.