TY - JOUR
T1 - The effects of electronic coupling and solvent broadening on the intervalent electron transfer of a centrosymmetric mixed-valence complex
AU - Watson, David F.
AU - Bocarsly, Andrew Bruce
N1 - Funding Information:
We thank Z. Soos and M. Hennessy for their theoretical analysis, and T. Spiro for the use of his Raman instrumentation. This work was supported by the National Science Foundation under grant number CHE-9631380.
PY - 2001
Y1 - 2001
N2 - A three-dimensional nuclear coordinate representation of the intervalent electron transfer processes occurring in the trinuclear mixed-valence complex, [(NC)5Fe(II)-CN-Pt(IV)(NH3)4-NC-Fe(II)(CN) 5]4-, is discussed in terms of the degree of coupling between electronic states. The related dinuclear complex, (NC)5Fe(II)-CN-Pt(IV)-(NH3)5, has been synthesized and characterized by UV-vis and IR absorption spectroscopies, cyclic voltammetry, resonance Raman spectroscopy, and single crystal X-ray diffraction. The visible absorption spectra and time-dependent resonance Raman intensity analyses of the two complexes are compared with regard to the amount of electronic coupling in the trinuclear complex. The absorption spectrum of the trinuclear complex has been fit to a model, which includes a solvent broadening parameter. Based on this fit, the total reorganization energy of the photoinduced intervalent electron transfer has been calculated to be approximately 75% outer sphere.
AB - A three-dimensional nuclear coordinate representation of the intervalent electron transfer processes occurring in the trinuclear mixed-valence complex, [(NC)5Fe(II)-CN-Pt(IV)(NH3)4-NC-Fe(II)(CN) 5]4-, is discussed in terms of the degree of coupling between electronic states. The related dinuclear complex, (NC)5Fe(II)-CN-Pt(IV)-(NH3)5, has been synthesized and characterized by UV-vis and IR absorption spectroscopies, cyclic voltammetry, resonance Raman spectroscopy, and single crystal X-ray diffraction. The visible absorption spectra and time-dependent resonance Raman intensity analyses of the two complexes are compared with regard to the amount of electronic coupling in the trinuclear complex. The absorption spectrum of the trinuclear complex has been fit to a model, which includes a solvent broadening parameter. Based on this fit, the total reorganization energy of the photoinduced intervalent electron transfer has been calculated to be approximately 75% outer sphere.
KW - Electronic coupling
KW - Mixed-valence complex
KW - Resonance Raman
KW - Solvent broadening
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U2 - 10.1016/S0010-8545(00)00276-9
DO - 10.1016/S0010-8545(00)00276-9
M3 - Review article
AN - SCOPUS:0035139909
SN - 0010-8545
VL - 211
SP - 177
EP - 194
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
IS - 1
ER -