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Abstract:

The NIR donor-acceptor charge transfer (DACT) bands of the series of trinuclear complexes trans-[(NC)5FeII/III(μ- CN)RuIIL4(μ-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)5Co III(μ-CN)RuII(py)4(μ-NC)Fe III(CN)5]4-, whose preparation is reported here for the first time. The analysis of the NIR spectra of the symmetric trans-[(NC)5FeIII(μ-CN)RuIIL 4(μ-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-Ru III-FeIII (or FeII-RuIII-Co III) electronic isomers are not thermally accessible. One-electron reduction leads to asymmetric trans-[(NC)5FeII(μ-CN) RuIIL4(μ-NC)FeIII(CN)5] 5- compounds with potentially two DACT bands involving the Ru II 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. © 2006 American Chemical Society.

Registro:

Documento: Artículo
Título:Donor-acceptor interactions and electron transfer in cyano-bridged trinuclear compounds
Autor:Alborés, P.; Rossi, M.B.; Baraldo, L.M.; Slep, L.D.
Filiación:Departamento de Química Inorgánica, Analítica Y Química Física, INQUIMAE, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Año:2006
Volumen:45
Número:26
Página de inicio:10595
Página de fin:10604
DOI: http://dx.doi.org/10.1021/ic061202k
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v45_n26_p10595_Albores

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Citas:

---------- APA ----------
Alborés, P., Rossi, M.B., Baraldo, L.M. & Slep, L.D. (2006) . Donor-acceptor interactions and electron transfer in cyano-bridged trinuclear compounds. Inorganic Chemistry, 45(26), 10595-10604.
http://dx.doi.org/10.1021/ic061202k
---------- CHICAGO ----------
Alborés, P., Rossi, M.B., Baraldo, L.M., Slep, L.D. "Donor-acceptor interactions and electron transfer in cyano-bridged trinuclear compounds" . Inorganic Chemistry 45, no. 26 (2006) : 10595-10604.
http://dx.doi.org/10.1021/ic061202k
---------- MLA ----------
Alborés, P., Rossi, M.B., Baraldo, L.M., Slep, L.D. "Donor-acceptor interactions and electron transfer in cyano-bridged trinuclear compounds" . Inorganic Chemistry, vol. 45, no. 26, 2006, pp. 10595-10604.
http://dx.doi.org/10.1021/ic061202k
---------- VANCOUVER ----------
Alborés, P., Rossi, M.B., Baraldo, L.M., Slep, L.D. Donor-acceptor interactions and electron transfer in cyano-bridged trinuclear compounds. Inorg. Chem. 2006;45(26):10595-10604.
http://dx.doi.org/10.1021/ic061202k