Syntheses, Structures and Solid-State Properties of MMX Mixed-Valence Chains, [NiII/III2(RCS2)4I]∞ (R = Et, n-Pr and n-Bu): Evidence of a Spin-Peierls Transition

The partial oxidation of [Ni(II/II)(2)(RCS(2))(4)] (R = Et (1), n-Pr (2), and n-Bu (3)) with iodine affords the MMX chain compounds [Ni(II/III)(2)(RCS(2))(4)I](infinity) (R = Et (4), n-Pr (5), and n-Bu (6)), respectively. The crystal structures of 4-6 consist of neutral one-dimensional (1-D) chains with a repeating -Ni-Ni-I- unit. The room-temperature (RT) structure of 4 indicates a charge-polarization (CP) state {-Ni((2.5-delta)+)-Ni((2.5+delta)+)-I(-)-Ni((2.5-delta)+)-Ni((2.5+delta)+)-I(-)- (delta << 0.5)} close to an averaged valence state judged by the Ni-I distances. In contrast, 5 and 6 exhibit a 3-fold periodicity of a -Ni-Ni-I- unit due to the disorder of the dithiocarboxylato ligands. Compounds 4-6 show typical semiconducting behavior and exhibit an intense sharp absorption band centered at 5400 cm(-1), which is attributed to a Mott-Hubbard gap due to a relatively large on-site Coulomb repulsion energy U of the nickel atoms. The high-temperature magnetic susceptibilities of 4-6 can be described by a 1-D Heisenberg antiferromagnetic chain model with |J|/k(B) ranging from 898(2) to 939(3) K. Compounds 4 and 5 undergo a spin-Peierls (SP) transition at relatively high T(sp) = 47 and 36 K, respectively, which are accompanied by superlattice reflections corresponding to a 2-fold -Ni-Ni-I- period below T(sp). By determining the superstructure of 4 at 26 K, we conclude that the valence-ordered state changes from the CP in the RT phase to the alternate charge-polarization (ACP) state of -Ni((2.5-delta)+)-Ni((2.5+delta)+)-I(-)-Ni((2.5+delta)+)-Ni((2.5-delta)+)-I(-)- in the SP phase. Such a spin-Peierls transition could not be observed for 6.