ABSTRACT Preparations of bulky, non-planar metal (M = Zn(II), In(III), Tl(III), V(IV), Nb(V), Mo(IV), W(IV), Re(V), Sn(IV) and Sb(V)) complexes with C3S52- and C3Se52- ligands are described. Their molecular and crystal structures, spectroscopies and electrochemical properties are shown. Many of them exhibit molecular interactions among the bulky anion moieties through sulfur-sulfur non-bonded contacts (<3.7 Å) in the solid state. Cyclic voltammetry of these complexes indicates low oxidation potentials. Oxidation of them by reactions with oxidizing agents, such as iodine, the ferrocenium cation and the tetrathiafulvalenium radical cation or electrolysis affords solids of partially oxidized species. Their spectroscopies and crystal structures for some oxidized complexes are described. They contain unpaired electrons in highly extended molecular interaction networks of the oxidized anion moieties through S-S and Se-Se non-bonded contacts. They behave as electrical conductors; some oxidized species exhibit electrical conductivities of 1 - 10-1 S cm-l for compacted pellets at room temperature.
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