| Abstract
| - The choice of appropriate electron donors (D) and acceptors (A) allows for the first time the simultaneousobservation of Mulliken charge-transfer states, [D,A], that can coexist in reversible equilibrium with electron-transfer states, {D+•,A-•}, for various diamagnetic organic redox dyads. The theoretical analysis based on the(two-state) Mulliken−Hush analysis of the intervalence optical transition, together with the spectral identificationof the transient ion-radical pairs of D+• and A-•, leads to the construction of the unusual potential-energysurface consisting of a single minimum without any reorganizational barrier for electron-transfer cross-exchanges with driving forces close to the isergonic limit. The mechanistic implications of this directdemonstration of the facile charge-transfer/electron-transfer interchange are discussed.
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