UV-Vis absorption spectra of one-electron reduction products and (MLCT)-M-3 excited states of [(ReCl)-Cl-I(CO)(3)-(N, N)] (N, N = 2,2'-bipyridine, bpy; 1,10-phenanthroline, phen) have been measured by low-temperature spectroelectrochemistry and UV-Vis transient absorption spectroscopy, respectively, and assigned by open-shell TD-DFT calculations. The characters of the electronic transitions are visualized and analyzed using electron density redistribution maps. It follows that reduced and excited states can be approximately formulated as [(ReCl)-Cl-I(CO)(3)(N,N-center dot)] and /[(ReCl)-Cl-II(CO)(3)(N,N-center dot)], respectively. UV-Vis spectra of the reduced complexes are dominated by IL transitions, plus weaker MLCT contributions. Excited-state spectra show an intense band in the UV region of similar to 50% IL origin mixed with LMCT (bpy, 373 nm) or MLCT (phen, 307 nm) excitations. Because of the significant IL contribution, this spectral feature is akin to the principal IL band of the anions. In contrast, the excited-state visible spectral pattern arises from predominantly LMCT transitions, any resemblance with the reduced-state visible spectra being coincidental. The Re complexes studied herein are representatives of a broad class of metal alpha-diimines, for which similar spectroscopic behavior can be expected. (C) 2011 Elsevier B. V. All rights reserved.