Atomic force microscopy (AFM) of porphyrin aggregates formed on silica from acidic aqueous
solution is used to investigate the basis for the previously reported counterion dependence of the optical
spectra of aggregates of H2TCPP2+, the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP). Resonance
light scattering confirms the presence of excitonically coupled porphyrin aggregates in solutions of
H2TCPP2+ in both aqueous HCl and HNO3. Aggregates formed in aqueous HNO3 solutions show resonance
light scattering (RLS) at wavelengths within both the H and J aggregate absorption bands and are imaged
on the surface of silica as nanorods about 3 to 4 nm in height. H2TCPP2+ aggregates in aqueous HCl
solution exhibit RLS when excited within the blue-shifted Soret band (H band) and produce AFM images
on silica of ring-shaped structures ranging from about 200 to 2000 nm in diameter. Fluorescence excitation
and emission spectra reveal quenching of the Q-band emission in the aggregates at a pH less than 1 and
confirm the existence of a single species, assigned to a dimer, at a pH just above 1. The morphology of
the nanostructures as revealed by AFM provides insight into the structural basis for the counterion-dependent
optical properties of H2TCPP2+ aggregates.
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