Abstract
Absorption and luminescence spectroscopy of the title compounds have been studied in single crystals, PVA foils and alcohol solutions. Particular attention has been given to crystal sites with defined symmetry (D 3 and C 2 for Fe, Ru, Os). The effect of 4,4′ substitution in bpy has been studied for Fe, Ru, and OS complexes and significant intensity flow out of the ligand absorption bands into the metal to ligand charge transfer bands has been found for Ru and Os, consistent with back π-bonding. CD, CPL, MCD, MCPL and time resolved luminescence spectroscopy have been used to help make assignments. All of these data support a delocalized description of the luminescent states, except in fluid solutions where a viscosity dependent relaxation to a localized charge transfer state occurs. The first detailed investigation of the excited states of chromium (III) trisbipyridine in crystals is reported.
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