This study presents the preparation of a novel tetra-substituted phthalonitrile (1) namely 3,6-bis(hexyloxy)-4,5-bis(4-(trifluoromethoxy)phenoxy)phthalonitrile (1) and its metal-free (2)/metal {M= Zn (3), Cu (4), Co (5), Lu(CH3COO) (6), Lu (7)} phthalocyanines....

Photodynamic therapy (PDT) applications carried out with the assistance of ultrasound have attracted significant attention in recent years. The use of phthalocyanines, which are an important component as photosensitizers in PDT, is becoming more important day by day. In therapeutic applications, phthalocyanines can promote the production of reactive oxygen species. Motivated by this fact, the syntheses of metal-free (2), gallium (3), and indium (4) phthalocyanines have been achieved by substituting 4-(cinnamyloxy)phthalonitrile for the first time to evaluate their therapeutic applications. Additionally, photophysicochemical, sonophotochemical, and in vitro evaluations of phthalocyanines have been reported. To the best of our knowledge, this is the first study of the use of phthalocyanines with different metal ions as potential photosensitizers for sonophotodynamic therapy (SPDT) applications in gastric cancer cell lines. The results show that the quantum yield of the generation of singlet oxygen increased in sonophotochemical studies (Φ Δ = 0.55 (2), 0.85 (3), 0.96 (4)), compared to photochemical studies (Φ Δ = 0.22 (2), 0.61 (3), 0.78 (4)). The density functional theory (DFT) results are in good agreement with the experimental results and suggest increased reactivity of phthalocyanines 3 and 4 in various redox processes, thus implying their applicability and usefulness as potential therapeutic agents. These phthalocyanines are effective sensitizers for PDT, sonodynamic therapy (SDT), and SPDT against MKN-28 gastric cancer cell line in vitro. All three treatments decreased cell viability and induced apoptosis in the gastric cancer cell line. However, indium phthalocyanine (4)-mediated SPDT was a more effective treatment modality compared to indium phthalocyanine (4)-mediated PDT and SDT. Also, indium phthalocyanine (4) was found to be a more effective sensitizer to activate apoptosis compared to the other phthalocyanines. To sum up, phthalocyanine-mediated SPDT enhances the cytotoxic effect on gastric cancer cells more than the effect of SDT or PDT alone.

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State-of-the-art computational tools were used to investigate the photophysical properties of polyfluorinated phthalocyanines (Pc) to predict their potential use as photosensitizers in photodynamic therapy. The main factors, such as the identity of the metal ion, the effect of substituents, the environment, and solvent effects that enhance the efficiency of phthalocyanines as photosensitizers, were considered, particularly taking into account their influence on the triplet-state energy and intersystem crossing probability. The population of the triplet state ultimately determines the phthalocyanine's propensity to activate singlet oxygen, which is responsible for inducing death of the cancer cell. Time-dependent density functional theory was used to elucidate the photophysical properties of pentafluorobenzyloxysubstituted phthalocyanines (R 2 Pc) as well as their unsubstituted analogues. Vibrational and dynamic effects influencing the absorption and emission spectra were included by sampling the potential energy surfaces via the Wigner distribution approach. Furthermore, the intersystem crossing pathways were analyzed by using the singlet−triplet band gap and the spin−orbit coupling constant. Finally, the singlet oxygen generation capability was experimentally verified for the R 2 −ZnPc complex both in DMSO and in different ratios of DMSO/water mixtures. The singlet oxygen quantum yield of R 2 -ZnPc in DMSO was also evaluated and compared with that of the unsubstituted ZnPc.

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