Aggregation of Zinc Protoporphyrin in Anodized Aluminum Oxide (AAO) Nanoporous Environments

The aggregation behavior of zinc protoporphyrin (ZnPP) inside nanoporous environments of anodized aluminum oxide (AAO) has been investigated through observation of the variation of UV/visible absorption and emission spectra of the system. The Soret band in the absorption spectrum of ZnPP/AAO thin‐film samples becomes much broader than that observed for ZnPP/THF solutions, and the relative intensity of the Q band is distinctly enhanced for the former. The broad Soret band overlaps the enhanced Q band increasingly as the degree of aggregation increases with increasing duration of immersion, with initial concentration of ZnPP/THF solutions, or with decreasing pore size of AAO nanotubes. A strong excitonic coupling between the Soret and Q transition dipoles causes the absorption spectrum of the ZnPP/AAO system to cover the entire visible spectral region. Emission spectra of ZnPP/AAO samples in the steady state contain multiple resolvable components assigned to monomer, dimer and higher aggregates. The observed systematic variation of emission spectra of ZnPP/AAO samples is consistent with the observation in absorption spectra of the system and reflects the significance of aggregation of ZnPP in a specific nanoporous environment.