Donor-Acceptor Interactions and Electron Transfer in Cyano-Bridged Trinuclear Compounds

ALBORES, P.; ROSSI, M. B.; BARALDO, L. M.; SLEP, L. D.

INORGANIC CHEMISTRY

American Chemical Society

Año: 2006 vol. 45 p. 10595 - 10604

0020-1669

The NIR donor-acceptor charge transfer (DACT) bands of the series of trinuclear complexes trans-[(NC)5FeII/III(-CN)RuIIL4(-NC)FeIII(CN)5]5/4- (L= pyridine, 4-tert-butylpyridine, and 4-methoxypyridine) are analyzed in terms of a simplified molecular orbital picture that reflects the interaction between the donor and acceptor fragments. The degree of electronic coupling between the fragments is estimated by a full fit of the DACT band profiles according to a three-state model inspired in the Mulliken-Hush formalism. The information is complemented with determinations performed on the asymmetric heterotrinuclear species trans-[(NC)5CoIII(-CN)RuII(py)4(-NC)FeIII(CN)5]4-, whose preparation is reported here for the first time. The analysis of the NIR spectra of the symmetric trans-[(NC)5FeIII(-CN)RuIIL4(-NC)FeIII(CN)5]4- species reveals a low degree of mixing between the terminal acceptor fragments and the bridging moiety containing RuII, with H12 values between1.0 × 103 and 1.5 × 103 cm-1. The reorganization energy contributions seem to be the same for the three species, even when the spectra were recorded in different media. This observation also applies for the CoIII-substituted compound. The computed potential energy surfaces (PES) of the ground state for these complexes show only one stationary point, suggesting that the FeII-RuIII-FeIII (or FeII-RuIII-CoIII) electronic isomers are not thermally accessible. One-electron reduction leads to asymmetric trans-[(NC)5FeII(-CN)RuIIL4(-NC)FeIII(CN)5]5- compounds with potentially two DACT bands involving the RuII and the FeII donor fragments. These species reveal a similar degree of electronic mixing but the PES shows three minima. We explore the role of the bridging fragment in the long-range thermally induced electron transfer between the distant iron centers. The results suggest that superexchange and hopping might become competitive paths, depending on the substituents in the bridging fragment.