Exciton Localization on Ru-Based Photosensitizers Induced by Binding to Lipid Membranes.

The characterization of electronic properties of metal complexes embedded in membrane environments is of paramount importance to develop efficient photosensitizers in optogenetic applications. Molecular dynamics and QM/MM simulations together with quantitative wave function analysis reveal a directional electronic redistribution of the exciton formed upon excitation of [Ru(bpy)(bpy-C17)] when going from water to a lipid bilayer, despite the fact that the media influence neither the metal-to-ligand charge-transfer character nor the excitation energy of the absorption spectra. When the photosensitizer is embedded into the DOPC lipid membrane, exciton population is mainly located in the bypyridyl sites proximal to the positively charged surface of the bilayer due to electrostatic interactions. This behavior shows that the electronic structure of metal complexes can be controlled through the binding to external species, underscoring the crucial role of the environment in directing the electronic flow upon excitation and thus helping rational tuning of optogenetic agents.