So far, symmetry-breaking charge separation (SB-CS) has been observed with a limited number of chromophores and is usually inhibited by the formation of an excimer. We show here that thanks to fine-tuning of the interchromophore coupling via structural control, SB-CS can be operative with pyrene, despite its high propensity to form an excimer. This is realized with a bichromophoric system consisting of two pyrenes attached to a crown ether macrocycle, which can bind cations of different sizes. By combining stationary and time-resolved spectroscopy together with molecular dynamics simulations, we demonstrate that the excited-state dynamics can be totally changed depending on the binding cation. Whereas strong coupling leads to rapid excimer formation, too weak coupling results in noninteracting chromophores. However, intermediate coupling, achieved upon binding of Mg2+, allows for SB-CS to be operative.

Photoinduced symmetry-breaking charge separation (SB-CS) results in the generation of charge carriers through electron transfer between two identical molecules, after photoexcitation of one of them. It is usually studied in systems where the two reacting moieties are covalently linked. Examples of photoinduced bimolecular SB-CS with organic molecules yielding free ions remain scarce due to solubility or aggregation issues at the high concentrations needed to study this diffusion-assisted process. Here we investigate the excited-state dynamics of perylene (Pe) at high concentrations in solvents of varying polarity. Transient absorption spectroscopy on the subnanosecond to microsecond timescales reveal that self-quenching of Pe in the lowest singlet excited state leads to excimer formation in all solvents used. Additionally, bimolecular SB-CS, resulting in the generation of free ions, occurs concurrently to excimer formation in polar media, with a relative efficiency that increases with the polarity of the solvent. Moreover, we show that SB-CS is most efficient in room-temperature ionic liquids due to a charge-shielding effect leading to a larger escape of ions and due to the high viscosity that disfavours excimer formation.