Etalon-Assisted Study of the Strong CO Ligand Vibrations of the fac-[Re(CO)3(bpy)(CH3CN)]+ Octahedral Complex.

Abstract

The strong CO ligand vibrations of an octahedral complex, fac-[Re (CO)3(bpy)(CH3CN)]+, in acetonitrile are observed at 2040 and 1932 cm-1. Facial rhenium tricarbonyl systems offer very strong and isolated CO vibrations with the potential for interactions between these vibrations. This work first identifies the dominant ion-pair species using attenuated total reflection infrared (ATR-IR) absorption spectra on a dilution series and then determines the strength of these CO ligand vibrations (as isolated vibrations) with a combination of ATR-IR and etalon-based measurements that determine the absolute complex index of refraction of the solution. Finally, the etalon experiments are modeled to study the interaction between vibrations, which is a property not embedded in the solution's complex index of refraction. The ATR-IR spectra are accomplished on a dilution series as well as a larger set of spectra as these solutions evaporated. The A'(1) CO ligand band at 2040 cm-1 is fit with a sum of three Lorentzian functions characterizing the distribution of free, solvent-separated, and contact ion pairs of this octahedral complex vs concentration. The other CO ligand band at 1932 cm-1 is broader and complicated by the dynamics of vibrational interactions, the unresolved splitting of the A'(2) and A″ CO vibrations, and ion-pair speciation. The etalon transmission measurements vs angle were on a 0.029 M solution, and Rabi splittings of 19 and 38 cm-1 were observed for the A'(1) CO vibration and the unresolved A'(2) + A″ CO vibrations, respectively. The great strength of the CO ligand vibrations is evident despite the use of a dilute solution. Integrated band intensities are reported in comparison to hybrid density functional calculations for isolated vibrations. Then, the observed Rabi splittings are modeled to obtain the coupling strength of the CO ligand vibration with etalon cavity modes and with each other. In summary, this work develops a method to determine the concentration of these solutions from the ATR-IR spectrum, characterizes the ion-pairing, shows that the index of refraction is not constant in the IR spectral region of interest, and develops an interaction Hamiltonian that characterizes cavity-vibration and vibration-vibration coupling.