Recent investigations in this laboratory have shown that d6 rhodium(III) complexes of the types [Rh(phen)3]3+ and  [Rh(phen')3]3+ where phen = 1,10-phenanthroline, phen' = substituted 1,10-phenanthroline, exhibit weak interactions with dioxygen at cryogenic temperatures that affect the photophysical behaviors of these complexes.  These dioxygen-complex interactions are tunable chemically by choice of ligands and ligand substituents (e.g., phen or phen') and also physically by temperature and dioxygen pressure. The tuning effects are achieved by regulating the relative positions of and thermal access to the pp*, dd, and dp* triplet excited states of these systems.

Tuning and spectroscopic interrogation of weak dioxygen-complex interactions in tris diimine complexes of rhodium(III) at cryogenic temperatures

243rd National Meeting (2012)

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