Electroabsorption studies of (NC)5FeCNOs(NH3)5- show that light-induced metal-to-metal charge transfer is accompanied by a dipole moment change of -12.5 ± 1.5 D along the charge-transfer axis. This change corresponds to an effective one-electron transfer distance of 2.5 ± 0.3 A, i.e., less than half the geometric distance from iron to osmium. The charge-transfer distance revision has profound effects upon estimates for solvent reorganization and nonadiabatic electronic coupling energies. The distance revision decreases the former from 7000 to 2200 cm-1 and increases the latter from 1260 to 2600 cm-1. Reliable estimates for both, of course, are required in order to understand light-induced electron-transfer kinetics.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry