American Chemical Society
Journal of the American Chemical Society
Intervalence absorption bands appearing in the diagnostic near-IR region are consistently observed in the electronic spectra of mixed-valence systems containing a pair of aromatic redox centers (Ar•+/Ar) that are connected by two basically different types of molecular bridges. The through-space pathway for intramolecular electron transfer is dictated by an o-xylylene bridge in the mixed-valence cation radical 3•+ with Ar = 2,5-dimethoxy-p-tolyl (T), in which conformational mobility allows the proximal syn disposition of planar T•+/T redox centers. Four independent experimental probes indicate the large through-space electronic interaction between such cofacial Ar•+/Ar redox centers from the measurements of (a) sizable potential splitting in the cyclic voltammogram, (b) quinonoidal distortion of T•+/T centers by X-ray crystallography, (c) “doubling” of the ESR hyperfine splittings, and (d) a pronounced intervalence charge-resonance band. The through (br)-bond pathway for intramolecular electron transfer is enforced in the mixed-valence cation radical 2a•+ by the p-phenylene bridge which provides the structurally inflexible and linear connection between Ar•+/Ar redox centers. The direct comparison of intramolecular rates of electron transfer (kET) between identical T•+/T centers in 3•+ and 2a•+indicates that through-space and through-bond mechanisms are equally effective, despite widely different separations between their redox centers. The same picture obtains for 3•+ and 2a•+from theoretical computations of the first-order rate constants for intramolecular electron transfer from Marcus−Hush theory using the electronic coupling elements evaluated from the diagnostic intervalence (charge-transfer) transitions. Such a strong coherence between theory and experiment also applies to the mixed-valence cation radical 7•+, in which the aromatic redox S center is sterically encumbered by annulation.