Solvent-Driven Self-Organization of Meso-Substituted Porphyrins: Morphological Analysis from Fluorescence Lifetime...

A morphological analysis of different thin films of meso-tetra-p-(di-p-phenylamino)phenylporphyrin, HT(TPA)P, was made by fluorescence lifetime imaging microscopy (FLIM) and scanning electron microscopy (SEM). A comprehensive study of HT(TPA)P was undertaken through UV/vis absorption and fluorescence techniques in different solvents, solvent mixtures and in thin films. In solution, occurrence of intramolecular energy transfer from the triphenylamine (TPA) moieties to the porphyrin core, with quenching efficiencies in the order of 94-97%, is observed. The energy transfer rate constants are determined assuming Förster's dipole-dipole and Dexter's electron exchange mechanisms. In drop-cast-prepared thin films, from samples with different solvent mixtures, the photoluminescence (PL) quantum yield (Φ_PL) decreases ∼1 order of magnitude compared to the solution behavior. FLIM and SEM experiments showed the self-organization and morphology of HT(TPA)P in thin films to be highly dependent on the solvent mixture used to prepare the film. In chloroform, the solvent's evaporation results in the formation of elongated and overlapped microrod structures. Introduction of a cosolvent, namely, a polar cosolvent, promotes changes in the morphology of the self-assembled structures, with the formation of three-dimensional spherical structures and hollow spheres. HT(TPA)P dispersed in a polymer matrix shows enhanced Φ_PL values when compared to the drop-cast films. FLIM images showed coexistence of three different states or domains: aggregated, interface, and nonaggregated or less-aggregated states. This work highlights the importance of FLIM in the morphological characterization of heterogeneous films, together with the photophysical characterization of nano- and microdomains.