80584-12-9Relevant articles and documents
Outer-sphere charge transfer in mixed-metal ion pairs
Curtis, Jeff C.,Meyer, Thomas J.
, p. 1562 - 1571 (1982)
Outer-sphere charge-transfer (OSCT) transitions have been observed in water for a series of mixed-metal ion pairs: [MII(CN6),RuIII(NH3) 5(L)]- (M = Fe, Ru, Os; L = pyridine or a substituted pyridine). After developing an appropriate thermochemical cycle it is possible to show that as expected from theory, the energies of the optical transitions vary with ΔHIPo′ where ΔHIPo′ is the enthalpy difference associated with charge transfer within the ion pair, [MII(CN)6,RuIII(NH3) 5(L)]- → [MIII(CN)6,RuII(NH3) 5(L)]-. A detailed analysis of the OSCT absorption bands leads to a number of important conclusions, including (1) the presence of electronic structure is due to the effects of spin-orbit coupling at the MIII(CN)63- d5 core following optical excitation, (2) the extent of electronic coupling between electron-donor and -acceptor sites is only slightly dependent on M in M(CN)64-, and (3) the most probable outer-sphere structure involves contact between M(CN)64- and an ammine face of the complexes Ru(NH3)5(L)3+.
