Influence of extrinsic factors on electron transfer in a mixed-valence Fe(2+)/Fe(3+) complex: experimental results and theoretical considerations.

The crystal structure of the mixed-valence complex (NEt(4))[Fe(2)(salmp)(2)].xMeCN(crystal) (x = 2,3) [1].xMeCN(crystal) was determined at temperatures between 153 and 293 K. The complex shows distinct Fe(2+) and Fe(3+) sites over this temperature interval. Variable temperature Mössbauer spectra confirm the valence-localized character of the complex. In contrast, spectroscopic investigation of powder samples generated from [1].xMeCN(crystal) indicate the presence of a valence-averaged component at temperatures above 150 K. To elucidate this apparent contradiction we have conducted a variable-temperature Mössbauer investigation of different forms of 1, including [1].xMeCN(crystal), [1].2DMF(crystal), [1].yMeCN(powder), and solution samples of 1 in acetonitrile. The low-temperature Mössbauer spectra of all forms are virtually identical and confirm the valence-localized nature of the S = (9)/(2) ground state. The high-temperature spectra reveal a subtle control of electron hopping by the environment of the complexes. Thus, [1].xMeCN(crystal) has valence-localized spectra at all explored temperatures, [1].2DMF(crystal) exhibits a complete collapse into a valence-averaged spectrum over a narrow temperature range, the powder exhibits partial valence averaging over a broad temperature interval, and the solution sample shows at 210 K the presence of a valence-averaged component in a minor proportion. The spectral transformations are characterized by a coexistence of valence-localized and valence-averaged spectral components. This phenomenon cannot be explained by intramolecular electron hopping between the valence-localized states Fe(A)(2+)Fe(B)(3+) and Fe(A)(3+)Fe(B)(2+) in a homogeneous ensemble of complexes, but requires relaxation processes involving at least three distinguishable states of the molecular anion. Hopping rates for [1].2DMF(crystal) and [1].yMeCN(powder) have been determined from spectral simulations, based on stochastic line shape theory. Analysis of the temperature dependences of the transfer rates reveals the existence of thermally activated processes between (quasi) degenerate excited states in both forms. The preexponential factors in the rate law for the hopping processes in the [1].yMeCN(powder) and [1].2DMF(crystal) differ dramatically and suggest an important influence of the asymmetry of the complex environment (crystal) on intramolecular electron hopping. The differences between the spectra for the crystalline sample [1].xMeCN and those for powders generated under vacuum from these crystals indicate that solvate depletion has a profound effect on the dynamic behavior. Finally, two interpretations for the three states involved in the relaxation processes in 1 are given and critically discussed (salmp = bis(salicyledeneamino)-2-methylphenolate(3-)).