Diastereomerically Differentiated Excited State Behavior in Ruthenium(II) Hexafluoroacetylacetonate Complexes of Diphenyl Thioindigo Diimine

Mono- and diruthenium hexafluoroacetylacetonate (hfac) complexes of the thioindigo-N,N'-diphenyldiimine chelating ligand 3 have been prepared. The thioindigo diimine ligand binds to ruthenium in a bidentate fashion in the mononuclear compound 2 and serves as a bidentate chelating bridging ligand in the diruthenium complexes 1a and 1b. Compound 2 was isolated as a racemic mixture while the diruthenium complexes were isolated as the meso (ΔΛ) 1a and rac (ΔΔ and ΛΛ) 1b diastereomers. In-depth structural characterization of the compounds was performed, including X-ray crystallography, 1 H, 13 C, and 19 F nuclear magnetic resonance (NMR) spectroscopy, and 2D NMR correlation experiments. Electrochemical properties were evaluated utilizing cyclic voltammetry. Ground state optical properties of the complexes were examined using UV-visible spectroscopy and spectroelectrochemistry. The excited state dynamics of the series were investigated by ultrafast transient absorption spectroscopy. Variable temperature NMR experiments demonstrated that the rac diruthenium compound 1b undergoes conformational exchange with a rate constant of 8700 s -1 at 298 K, a behavior that is not observed in the meso diastereomer 1a. The series of complexes possess metal-to-ligand charge transfer (MLCT) absorption bands in the near-infrared (λ max 689-783 nm). The compounds do not display photoluminescence in room temperature solution-phase experiments or in experiments at 77 K. Transient absorption spectroscopy measurements revealed excited states with picosecond lifetimes for 1a, 1b, and 2, and spectroelectrochemical experiments confirmed assignment of the transient species as arising from MLCT transitions. Unexpectedly, the transient absorption measurements revealed disparate time constants for the excited state decay of diastereomers 1a and 1b.