A Temperature Dependence Study of 35Cl Nuclear Quadrupole Resonance Frequencies in Some Hexachloroplatinate(IV) Hexahydrates

Abstract

The temperature dependence of 35Cl NQR frequencies was investigated in various hexachloroplatinate( IV) hexahydrates containing the following divalent ions as counter cations: Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Ba(II). All of the compounds except the Cu(II) and Ba(II) salts yield a single 35Cl NQR line at all temperatures studied. For the Mn(II), Cu(II), and Ba(II) salts, the NQR frequencies are considerably shifted by deuteration. For the deuterated Mn(II) salt, two 35Cl NQR lines were observed whose relative peak-height intensities vary in dependence on the history of the thermal treatment of the sample. The very broad higher frequency line could be observed for a sample which had been at 77 K or below. It could not be observed for a sample which was cooled slowly to room temperature after it had been heated up to ca. 420 K. A structural phase transition was located at 135.6 and 129.4 K for the Cu(II) salt and its deuterated analog, respectively. The frequency shift by deuteration is discussed in relation to the strength of O - H ... CI type hydrogen bonds.