Pathway complexity in aqueous J-aggregation of an ionic BODIPY amphiphile

Abstract

A new amphiphilic boron-dipyrromethene (BODIPY) dye bearing a hydrophobic 2,3,4-tris(n-dodecyloxy) phenyl group at the meso-position and two hydrophilic cationic moieties at the boron was synthesized. This dye exhibited kinetically controlled and thermodynamically controlled aggregation pathways in aqueous solution, leading to the formation of two types of J-aggregates, i.e., the metastable Agg. I and thermodynamically more stable Agg. II. Further kinetic analysis of the spontaneous transformation from Agg. I to Agg. II indicated that Agg. I was an off-pathway aggregate species. Moreover, both Agg. I and Agg. II displayed J-aggregate characteristics with enhanced fluorescence quantum yields and shortened fluorescence lifetime with respect to that of the monomeric dye. In particular, Agg. II exhibited a narrowed and intense J-band, reflecting the strong excitonic coherence in the aggregate. Morphological studies revealed that Agg. I consisted of spherical nanoparticles, while Agg. II had a multilamellar vesicular structure. In addition, in the fluorescence spectra of Agg. I and Agg. II, an unexpected broad band at longer wavelength than that of the J-aggregate emission was observed, which could be ascribed to the possible formation of excimers in these J-aggregates in aqueous solution.