Measurement of ordered associate of protonated tetraphenylporphine formed at toluene/aqueous H2SO4 interface by attenuated total internal reflection spectroscopy with polarized light

Attenuated total internal reflection (ATR) spectroscopy with an s- or p-polarized visible light was examined for some species of protonated 5,10,15,20-tetraphenylporphine (tpp) at toluene/aqueous H2SO4 (3-6 mol dm−3) interface. Tpp initially dissolved in the toluene phase was diprotonated at the interface to form monomeric H2tpp2+, the absorption peak of which was 438 nm. At the same time, a long H2tpp2+ oligomer was formed, the absorption peak of which was 448 nm. The two interfacial species were transient. Just after their disappearance, a rod-shaped H2tpp2+ associate was formed at the interface, the absorption peak of which was 417 and 478 nm. The former and latter wavelengths corresponded to H- and J-bands of the associate, respectively. Theoretical calculation of the strength of electric field of light at the interface allowed one to estimate the interfacial concentration of the three species with measured reflection absorbance (AR). The monomeric H2tpp2+ and its oligomer were at sub-monolayer levels, whereas the associate was at a multilayer level. Reflection absorption anisotropy (KR), which was calculated from AR with the s- and p-polarized lights, was adopted for the evaluation of out-of-plane orientation of the interfacial species for the first time. The KR value suggested that the rod-shaped associate lay at the interface.