Resolving Resonant Electronic States in Chiral Metal Complexes by Raman Optical Activity Spectroscopy.

Chiral metal complexes exhibit rich photophysical properties and are important for applications ranging from biosensing to photocatalysis. We present a combined experimental and computational approach leading to information about energies and transition moments of excited electronic states, documented on two chiral metal complexes. The experimental protocol for measurement of the resonance Raman optical activity comprises multiple techniques, i.e., absorption, circular dichroism, and polarized and differential Raman scattering. An accurate formula for subtraction of the interfering circular dichroism/polarized Raman scattering effect is given. An analysis of the spectra based on density functional theory calculations unveils the geometric and electronic structures of the molecules. Such insight into molecular electronic states of chromophores may be useful for understanding and tuning photochemical properties of metal-containing complexes, biomolecules, and supramolecules.