Pseudo-para-dinitro[2.2]paracyclophane radical anion, a mixed-valence system poised on the Class II/Class III borderline.
Analysis of optical spectra of a pseudo-para-dinitro[2.2]paracyclophane radical anion using Marcus-Hush theory reveals that its off diagonal coupling element, H(ab), is large enough, relative to its reorganization energy, to change it from a localized class II compound to a delocalized class III compound by changing solvents. The optical spectra, along with frontier orbital analysis, show that the assumption that E(op) = 2H(ab) for class III compounds is not true in this case.
Nelsen
Stephen F
SF
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706-1396, USA. nelsen@chem.wisc.edu
Konradsson
Asgeir E
AE
Telo
João P
JP