| Abstract |
Optical absorption spectra of three dinitroaromatic radical anions, 2,7-dinitro-9,9-dimethylfluorene (1(center dot-)), 4,4 -dinitrobiphenyl (2(center dot-)), and 4,4 -dinitrotolane (3(center dot-)) in solvents THF, HMPA, and MeCN show both an unresolved broad band characteristic of charge-localized mixed valence species (Robin-Day classification Class II), and a vibronically structured band of the delocalized species (Class III). With decreasing solvent reorganization energy, a greater portion of the compounds become charge-delocalized. In particular, 1(center dot-) with the greatest coupling, is almost entirely composed of the delocalized species in all solvents. An intense Raman mode is used to identify the charge-bearing unit as the nitrobenzene moiety. Resonance Raman profiles are utilized to gain detailed information of vibrational modes. The out-of-phase ring lengthening stretch mode is observed to be enhanced at higher excitation energies, corresponding to the absorption band of the Class II species, while the in-phase ring lengthening stretch mode, a totally symmetric vibration, is most strongly enhanced in the absorption region of the Class III species. Resonance Raman profiles support the solvent-dependent coexistence of Class II and Class III molecules of the same chemical composition. |
