A Theoretical Analysis of the Potential Role of π–π Stacking Interactions in the Photoprotolytic Cycle of Firefly Luciferin

Firefly oxyluciferin is a photoacid that presents a pH‐sensitive fluorescence, which results from pH‐dependent changes on the conformation of self‐aggregated π–π stacking complexes. Luciferin is a derivative of oxyluciferin with very similar fluorescence and photoacidic properties. This similarity indicates that luciferin is also expected to be able to form π–π stacking complexes, but no pH‐sensitive fluorescence is found for this compound. Here, a theoretical approach is used to rationalize this finding. We have found that luciferin only forms π–π stacking complexes in the ground state at acidic pH. At basic pH and in the excited state, luciferin is present as a dianion. This species is not able to self‐aggregate, owing to repulsive electrostatic interactions. Thus, this emissive species is not subject to π–π stacking interactions; this explains its pH‐insensitive fluorescence.     

Theoretical Study of the Nontraditional Enol‐Based Photoacidity of Firefly Oxyluciferin

A theoretical analysis of the enol‐based photoacidity of oxyluciferin in water is presented. The basis for this phenomenon is found to be the hydrogen‐bonding network that involves the conjugated photobase of oxyluciferin. The hydrogen‐bonding network involving the enolate thiazole moiety is stronger than that of the benzothiazole phenolate moiety. Therefore, enolate oxyluciferin should be stabilized versus the phenolate anion. This difference in strength is attributed to the fact that the thiazole moiety has more potential hydrogen‐bond acceptors near the proton donor atom than the benzothiazole moiety. Moreover, the phenol‐based excited‐state proton transfer leads to a decrease in the hydrogen‐bond acceptor potential of the thiazole atoms. The ground‐state enol‐based acidity of oxyluciferin is also studied. This phenomenon can be explained by stabilization of the enolate anion through strengthening of a bond between water and the nitrogen atom of the thiazole ring, in an enol‐based proton‐transfer‐dependent way.     

Photoacidity of Indolinospirobenzopyrans in Water

The reversible isomerism of indolinospirobenzopyrans is perhaps among the most studied phenomena in the field of molecular switches. Although they began to gain attention as early as 70 years ago following the seminal work of Hirshberg and Fischer, who were the first to recognize their photochromic behaviours, their implementation as photoacids emerged prominently only in the last decade. In this Review, we contextualize the prerequisites underlying the photo-triggered proton release that occurs in these molecular switches, highlighting the most recent advances in their characterization and application as “metastable-state photoacids” in water.