Molecular engineering to enhance reactivity and selectivity in an ultrafast photoclick reaction


Fu Y, Simeth NA, Toyoda R, Brilmayer R, Szymanski W, Feringa BL


Angewandte Chemie International Edition


Angew Chem Int Ed Engl. 2023 Feb 17:e202218203.


Light-induced 9,10-phenanthrenequinone-electron-rich alkene (PQ-ERA) photocycloadditions are an attractive new type of photoclick reaction, featuring fast conversions and high biocompatibility. However, the tunability of the reaction was hardly investigated up to now. To this end, we explored the influence of substituents on both reaction partners and the reaction rate between the PQs and ERAs. We identified new handles for functionalization and discovered that using enamines as ERAs led to drastically enhanced rates (>5400 times faster), high photoreaction quantum yields (ΦP, up to 65 %), and multicolor emission output as well as high fluorescence quantum yield of the adducts (ΦF, up to 97%). Further investigation of the photophysical and photochemical properties provided the insights to design orthogonal reaction systems both in solution and on nanoparticle surfaces for ultrafast chemoselective functionalization by photoclick.


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