Observation of intramolecular vibrations cooperating with the magnetic phase transition in a nickel-bis-dithiolene compound

Abstract

A new one-dimensional (1-D) ion-pair compound, [1,7-bis(1-methylimidazolium)heptane][Ni(mnt)(2)](2) (mnt(2-) = maleonitriledithiolate), was synthesized and characterized structurally and magnetically. This compound shows a spin-Peierls-type transition at around 235 K. Its crystal structure belongs to the monoclinic system with space group C2/c and the magnetic [Ni(mnt)(2)](-) anions form uniform stacks in the high-temperature (HT) phase. The crystal undergoes a transformation into the triclinic space group P1 accompanied by the magnetic transition and the anion stacks become dimerized in the low-temperature (LT) phase. The entropy changes (ΔS) are estimated to be 0.772 J K(-1) mol(-1) for the spin-Peierls-type transition, from DSC data, which is much less than the spin entropy change (ΔS = R ln 2 ≈ 5.76 J K(-1) mol(-1)), indicating that a substantial short-range order persists above the transition temperature. The variable temperature IR spectra showed that the peak positions and intensities for the bands near 1160 and 725 cm(-1), which correspond respectively to the ν(C-C) + ν(C-S) mode of the mnt(2-) ligands and the rocking vibration mode of the methylene group γ(r)(CH(2)) in the cation moiety, undergo an abrupt change at around 240 K, close to the transition temperature. This observation demonstrates that the intramolecular vibrations of both the anion and the counter-cation probably couple with the spins to cooperate with the spin-Peierls-type phase transition in this 1-D spin system.