Quantitative investigations of the aggregation behaviour of hydrophobic anilino squaraine dyes through UV/vis spectroscopy and dynamic light scattering

In continuing studies of the aggregation behaviour of squaraine dyes in DMSO-water mixtures, we have examined a series of symmetrical anilino-based squaraines with increasing N-alkyl chain length (n-butyl, n-octyl, and n-dodecyl). The aggregation behaviour was assessed through UV/vis spectroscopic and Dynamic Light Scattering (DLS) studies with quantitative interpretation based on exciton theory. This class of N-alkyl squaraines forms two distinct solution aggregates, Type J and Type H, depending on the composition of the DMSO-water medium. DLS measurement of the aggregates in the Type J and Type H morphologies showed that (i) the particle diameter increased with increasing hydrophobicity; (ii) DMSO has a large effect on the aggregate size; (iii) Type J aggregates are of equal dimensions with Type H aggregates. Moreover, even though as the DMSO-water solvent composition is varied the UV/vis spectra of Type H and Type J aggregates remained unchanged, the number of molecules comprising each aggregate varies widely. It is proposed that the dynamic conversion (J →> H) results from intramolecular reorganization of individual molecules within the aggregate. Quantification of aggregation through DLS has further developed the "kinetic" versus "thermodynamic" control model of dye aggregation.Key words: squaraine, dynamic light scattering, DMSO-water mixtures, self-assembly, kinetic/thermodynamic control.