Solid-state properties of one-dimensional metals based on bis(oxalato)platinate anions with divalent cations

The crystal structures, superstructures, dc conductivity, optical properties, and thermopower of six linear-chain conductors of the type $M_{0.8}$[Pt(${\mathrm{C}}_2$${\mathrm{O}}_4$${)}_2$]⋅(M=Ni,Co,Zn,Fe,Mg,Mn), where M is a divalent metal (M=Ni,Co,Zn,Fe,Mg,Mn), have been studied. At high temperatures they form a common orthorhombic metallic phase (I) with conductivities of 30–200 (Ω cm${)}^{\mathrm{-}1}$ and thermopowers of 5–10 μV/K, with the lattice weakly modulated by the one-dimensional Peierls distortion. Below $T_1$, three compounds (Ni,Co,Zn) form a semiconducting phase (A-II) due to the ordering of the [M(${\mathrm{H}}_2$O${)}_6$${]}^{+2\mathrm{}}$ cations. As the cation superlattice is commensurate with the three-dimensional Peierls distortion, these salts transform at a lower temperature $T_2$ into a charge-density-wave phase (A-III). In the other three compounds (Fe,Mg,Mn), the cations order in a superlattice (phase B-II) which is incommensurate with both the average Pt-ion lattice and the three-dimensional Peierls distortion, and therefore no charge-density-wave state is formed. The influence of competing interactions is briefly discussed.