On the Aggregation Behaviour and Spectroscopic Properties of Alkylated and Annelated Boron-Dipyrromethene (BODIPY) Dyes in Aqueous Solution

Abstract

The tendency of boron-dipyrromethene (BODIPY) dyes to associate in water is well known, and usually a cause for inferior fluorescence properties. Synthetic efforts to chemically improve BODIPYs’ water solubility and minimize this problem have been numerous in the past. However, a deeper understanding of the phenomena responsible for fluorescence quenching is still required. Commonly, the spectroscopic behaviour in aqueous media has been attributed to aggregate or excimer formation, with such works often centring on a single BODIPY family. Herein, we provide an integrating discussion including very diverse types of BODIPY dyes. Our studies revealed that even subtle structural changes can distinctly affect the association behaviour of the fluorophores in water, involving different photophysical processes. The palette of behaviour found ranges from unperturbed emission, to the formation of H or J aggregates and excimers, to the involvement of tightly bound, pre-formed excimers. These results are a first step to a more generalized understanding of spectroscopic properties vs. structure, facilitating future molecular design of BODIPYs, especially as probes for biological applications.