mechanistic dominance for the past half century and more. In this Account, we illustrate how the simultaneous melding of all four key concepts allows sharp focus on the charge-transfer character of the critical encounter complex to evoke the latent facet of traditional electron-transfer mechanisms. To this

end, we exploit the intervalence (electronic) transition that invariably accompanies LY411575 ic50 the diffusive encounter of electron-rich organic donors (D) with electron-poor acceptors (A) as the experimental harbinger of the collision complex, which is then actually isolated and X-ray crystallographically established as loosely bound pi-stacked pairs of various aromatic and NVP-LDE225 olefinic donor/acceptor dyads with uniform interplanar separations of r(DA) = 3.1 +/- 0.2 angstrom. These X-ray structures, together with the spectral measurements of their

intervalence transitions, lead to the pair of important electron-transfer parameters, H-DA (electronic coupling element) versus lambda(r) (reorganization energy), the ratio of which generally defines the odd-electron mobility within such an encounter complex in terms of the resonance stabilization of the donor/acceptor assembly [1), A] as opposed to the reorganization-energy penalty required for its interconversion to the electron-transfer state [D+., A(-.)]. We recognize the resonance-stabilization energy relative to the intrinsic activation barrier as the mechanistic binding factor, Q = 2H(DA)/lambda(T), to represent the quantitative measure of the highly variable continuum of inner-sphere/outer-sphere interactions that are possible within various types of precursor complexes. First, Q << 1 identifies one extreme mechanism owing to slow electron-transfer rates that result from the dominance of the intrinsic activation barrier (AT) between the encounter and successor complexes. At the other extreme of Q BGJ398 concentration 1, the overwhelming dominance of the resonance stabilization (H-DA) predicts the odd-electron mobility between the donor and

acceptor to occur without an activation barrier such that bimolecular electron transfer is coincident with their diffusional encounter. In between lies a potentially infinite set of states, O < Q < 1 with opposing attractive and destabilizing forces that determine the location of the bound transition states along the reaction coordinate. Three prototypical potentialenergy surfaces evolve as a result of progressively increasing the donor/acceptor bindings (H-DA) extant in the precursor complex (at constant lambda(T)). In these cases, the “outer-sphere” mechanism is limited by the weak donor/acceptor coupling that characterizes the now classical Marcus outer-sphere mechanism.