The design and synthesis of a cooperative multichromophoric triad system which combines the large two-photon absorption properties of fluorene-cored bis-donor quadropolar dyes and the remarkable sensitizing properties of the porphyrin subunit (i.e. high intersystem crossing and ability to produce singlet oxygen by energy transfer to oxygen from its triplet excited state) is described. After irradiation the energy can be transferred from the quadrupolar chromophores to the porphyrin with an estimated 80% efficiency via a FRET process. Moreover both the two-photon absorption properties of the quadrupolar subunits and the sensitizing and fluorescence properties of the porphyrin are retained indicating that deleterious competing processes (such as photo-induced electron transfer) are prevented in such molecular architectures thanks to the implemented design. As a result, the two-photon absorption induced singlet oxygen generation efficiency of the triad in the NIR region is found to be enhanced by an order of magnitude as compared to the porphyin subunit. Potential applications of these porphyrin-based multichromophoric systems for photodynamic therapy based upon two-photon excitation in the NIR region might be possible since it overcomes the low two-photon absorption response of porphyrin while fully retaining their remarkable photosensitizing properties.
Highly efficient singlet oxygen generation, two-photon photodynamic therapy and melanoma ablation by rationally designed mitochondria-specific near-infrared AIEgens
