Due to their photoproperties and easy chemical functionalisations, phthalocyanines are amongst the most promising advanced photosensitisers for photodynamic therapy of cancer.
Molecular catalysts that combine high product selectivity and high current density for CO2 electrochemical reduction to CO or other chemical feedstocks are urgently needed. While earth-abundant metal-based molecular electrocatalysts with high selectivity for CO2 to CO conversion are known, they are characterized by current densities that are significantly lower than those obtained with solid-state metal materials. Here, we report that a cobalt phthalocyanine bearing a trimethyl ammonium group appended to the phthalocyanine macrocycle is capable of reducing CO2 to CO in water with high activity over a broad pH range from 4 to 14. In a flow cell configuration operating in basic conditions, CO production occurs with excellent selectivity (ca. 95%), and good stability with a maximum partial current density of 165 mA cm−2 (at −0.92 V vs. RHE), matching the most active noble metal-based nanocatalysts. These results represent state-of-the-art performance for electrolytic carbon dioxide reduction by a molecular catalyst.
Three Zn(II) phthalocyanines substituted by hydroxyl-terminated tetraethylene glycol chains have been synthesized. In order to evaluate the potential of these highly water-soluble phthalocyanines as type II-photosensitisers for photodynamic therapy, their structure–activity relationship was assessed by determining relevant photophysical and photochemical properties, such as their aggregation behaviour in aqueous buffers, their fluorescence properties and their efficiency with regard to the generation of singlet oxygen. In addition, evidence for a negligible interaction with plasma proteins in undiluted human plasma was obtained using a recently developed bioanalytical method and compared with the fluorescence quenching approach. These results combined with in vitro data regarding the phototoxicity of these phthalocyanines against HT-29 cancer cells provide evidence for the relevance of the non-peripherally substituted derivative for further in vivo investigations.
Four isomerically pure octasubstituted zinc phthalocyanines with variations in the attachment atom and positions of the substituents were selected for a systematic investigation of the effect of the substitution pattern on their electronic and spectroscopic properties. Effects which were investigated are the position, the electron donating and withdrawing properties, and the donating force of the substituent. The results are discussed and interpreted based on theoretical and experimental determination of the orbital levels. This work allows us to highlight which substitution patterns are the most suitable considering different common applications of phthalocyanines.