Ion-pairing and charge-transfer interactions between octacyano-molybdates(IV) and -tungstates(IV) and diquaternary bipyridines

摘要

New salts of formula [pq](2)[M(CN)(8)] [M = Mo or W, pq = paraquat (1,1'-dimethyl-4,4'-bipyridinediium)] have been synthesized. The systems [A(2+), M(CN)(8)(4-)] where A(2+) pq or dq (diquat, 6,7-dihydrodipyrido[1,2-a:2',1'-c]pyrazinediium), which show optical electron transfer from anion to cation, were studied. The first association constants in aqueous solution were determined spectroscopically and the properties of the ion-pair charge-transfer bands were used for calculation of the thermodynamic parameters of the electron transfer and construction of potential-energy curves on the basis of the Hush model. [References: 18]