Photosensitizing properties of squaraine dyes

Abstract

The present report summarises our results on the photophysical and photochemical investigations of a series of squaraine dyes which exhibit intense and sharp absorption bands in the visible and near infrared regions. The intramolecular charge-transfer transitions arising from the "donor-acceptor-donor" arrangements of these dyes have an interesting effect on their excited state properties. The major nonradiative decay process of squaraines is by rotation about the C-C bonds between the central cyclobutane unit and its neighbouring phenyl groups. Microencaging of one of the dyes by β-cyclodextrin or poly(4-vinylpyridine) was found to restrict this motion, bringing about up to 90-fold enhancement in its fluorescence yield. These aspects as well as the dynamics of charge transfer from the excited singlet state of some of the squaraine dyes to TiO₂ and the recombination of the injected charge with the dye radical cation are discussed.