Transition metal eight-coordination. VI. Isomerization through electronic and environmental effects. Electron spin resonance, magnetic circular dishroism and electronic spectra of octacyanotungstate(IV) and (V)

Abstract

The octacyanotungstate(IV) ion retains a dodecahedral geometry in aqueous solution, with the first spin-allowed d-d transition established as 'E 1 A, from magnetic circular dichroism spectroscopy. The other spin-allowed d-d transitions appear to be nondegenerate and are logically transitions to the ' B, and *A2 excited states. Both dodecahedral and antiprismatic ground states are evident for the octacyanotungstate(V) ion from electron spin resonance measurements, which indicate that the ground-state stereochemistry is both cation and solvent dependent.

EPR Study of MoVin the Tetragonal and Monoclinic Phases of Zirconia

“…This hypothesis awaits confirmation from a single-crystal study of Mo4-doped monoclinic ZrO . The relation between the EPR parameters and the energy levels of the Mo4 and Mo4 species resembles that found for the Mo4 species in the octocyanomolybdate(V) complex, Mo(CN)\ (33)(34)(35)(36). This eight-coordinated ion can exist in two different idealized configurations: dodecahedral and square antiprism.…”

A high-spin cyanide-bridged Mo6Mn9 cluster: crystal structure and magnetism

“…The precursor (n-Bu 4 N) 3 [Mo(CN) 8 ] was prepared according to literature method [47]. All other chemicals are of reagent grade and can be used without further purification.…”

The rationalized pathway from field-induced slow magnetic relaxation in CoII–WIV chains to single-chain magnetism in isotopological CoII–WV analogues

“…Octacyanidometallate precursors, K 4 [W IV (CN) 8 ]·2H 2 O and TBA 3 [W V (CN) 8 ]·2H 2 O (TBA = tetrabutylammonium cation), were prepared according to the published methods. 93,94…”