Continuum of Outer- and Inner-Sphere Mechanisms for Organic Electron Transfer. Steric Modulation of the Precursor Complex in Paramagnetic (Ion-Radical) Self-Exchanges

Transient 1:1 precursor complexes for intermolecular self-exchange between various organic
electron donors (D) and their paramagnetic cation radicals (D+•), as well as between different electron
acceptors (A) paired with their anion radicals (A-•), are spectrally (UV−NIR) observed and structurally
(X-ray) identified as the cofacial (π-stacked) associates [D, D+•] and [A-•, A], respectively. Mulliken−Hush
(two-state) analysis of their diagnostic intervalence bands affords the electronic coupling elements (HDA),
which together with the Marcus reorganization energies (λ) from the NIR spectral data are confirmed by
molecular-orbital computations. The HDA values are found to be a sensitive function of the bulky substituents
surrounding the redox centers. As a result, the steric modulation of the donor/acceptor separation (rDA)
leads to distinctive electron-transfer rates between sterically hindered donors/acceptors and their more
open (unsubstituted) parents. The latter is discussed in the context of a continuous series of outer- and
inner-sphere mechanisms for organic electron-transfer processes in a manner originally formulated by Taube
and co-workers for inorganic (coordination) donor/acceptor dyadswith conciliatory attention paid to
traditional organic versus inorganic concepts.