SYNTHESIS, CRYSTAL-STRUCTURE AND SPECTROSCOPIC STUDIES OF NEW CHARGE-TRANSFER COMPOUNDS OBTAINED BY REACTION OF TTF AND THE POLYOXOANION [MO6O19]2-

Two different tetrathiafulvalene radical cation salts of the [M06O19]2- polyoxoanion have been isolated and characterized. Compound 1 corresponds to the chemical formula (TTF)3[Mo6019]. The crystal structure shows a ID stack of the donor TTF molecule, and each stack fits into channels formed by the anions. Within the stack a chain of trimers is identified, the inter-trimeric distance being 3.51 Å. The I.R., electronic and XPS spectra suggest the compound to be a mixed-valence salt. The electrical conductivity at room temperature is ? = 10-4 Ohm-1 cm-1 Compound 2 corresponds to the chemical+formula (TTF)2[M06019] . The compound consists of isolated (TTF+o)2 dimers, interspersed with the polyoxoanions. In agreement with this crystal structure the compound is a diamagnetic insulator.