Aggregation Behavior of CHR-bis(BODIPY) Bichromophores in THF-water Mixtures: Effect of Linking Positions and Aryl-spacer Substituents.

Abstract

Aggregation-caused quenching effect (ACQ) greatly limits the practical use of many organic luminophores in biomedicine, optics and electronics. The comparative analysis of aggregation characteristics of CHR-bis(BODIPY) bichromophores 1-6 with R = H, Ph, MeOPh and various linking positions (α,α-; α,β-; β,β- and β',β'-) in THF-water mixtures with different water fractions or dye concentrations is first presented in this article. Both the linking style 1-4 and the arylation of the spacer with phenyl (Ph-) 5 or methoxyphenyl (MeOPh-) 6 substituents strongly affect the formation of luminophore aggregated forms in binary THF-water mixtures. The α,α-and β,β-isomers (1 and 3) form non-fluorescent H-type aggregates in THF-water mixtures with f_w > 70%. The α,β-; β',β'-isomers (2, 4) and the MeOPh-substituted β,β-bichromophore 6 are characterized by predominant formation fluorescent aggregates. All bichromophores are characterized by the presence of residual amounts of non-aggregated forms in binary mixtures with maximum water content. The results are useful for controlling the aggregation behavior and spectral characteristics of CHR-bis(BODIPY) bichromophores in aqueous-organic media, which is important in the development of biomarkers and PDT agents.