Cheng MHY, Bao S, Zheng G & Chen J
Journal of Porphyrins and Phthalocyanines, 2019
A pH-driven self-assembly of a simple aza-BODIPY was discovered in PBS solution, whereby ion-specific J-aggregated nanostructures were generated at very low dye concentration (2.5–20 μM). The aggregation process was investigated in different conditions (pH, temperature and time) by monitoring absorption spectral shifts and associated nanostructure morphological changes. The pH-driven self-assembly process demonstrated an instantaneous thermodynamic phenomenon associated with three characteristic structures, each with distinctive optical properties. When the sample was first formulated within a short time window, a thermodynamically less stable intermediate with an unusual morphology of triangular nanoplates and broad absorption was observed. The formation of these structures was independent of the ions in PBS solution (Na+, K+), thus indicating that the triangular structure was inherent to the anisotropic structure of aza-BODIPY scaffolds. The second structure associated with a metastable pathway generated a uniform population of spherical nanovesicles, while the third structure, generated through a more thermodynamically stable pathway consisted of fibers. The absorption spectra suggested that both spherical and fiber structures contributed to the J-aggregation band at 735 nm in the near infrared optical spectrum and their population in each formulation was concentration dependent. The results highlighted the significance of ion effects in self-assembly of aza-BODIPY and the mechanistic structural changes of the morphology. Furthermore, this fundamental discovery offers a versatile method for the self-assembly of aza-BODIPY J-aggregates as a new nanoplatform with potential photonic applications.