Photochemical action plots reveal the fundamental mismatch between absorptivity and photochemical reactivity Christopher Barner-Kowollik Centre for Materials Science, Queensland University of Technology (QUT), Australia Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Germany Over the last decade, our laboratory has employed monochromatic tunable laser systems to reveal a fundamental mismatch between the absorptivity of a chromophore and its photochemical reactivity in the vast majority of covalent bond forming reaction as well as specific bond cleavage reactions. Our data overturns the long-held paradigm that effective photochemical reactions are obtained in situations where there is strong overlap between the absorption spectrum and the emission wavelength. However – as we explore herein – the absorption spectrum of a molecule provides only information about singlet excitation and remains entirely silent on the accessibility of the critical triplet states, which dictate photochemical reactivity. We propose future avenues of enquiry on how action plots can be understood and explore how they are of key importance for tailoring photochemical applications in soft matter materials design with never before seen precision. References 1. Irshadeen, I.M.; Walden, S.L.; Wegener, M.; Truong, V.X.; Frisch, H.; Blinco, J.P.; Barner-Kowollik, C. J. Am. Chem. Soc. 2021, 143, 21113. 2. Menzel, J. P.; Feist, F.; Tuten, B.; Weil, T.; Blinco, J. P.; Barner-Kowollik, C. Angew. Chem. Int. Ed. 2019, 58, 7470. 3. Nardi, M.; Blasco, E.; Barner-Kowollik, C. J. Am. Chem. Soc. 2022, 144, 1094. 4. Kalayci, K.; Frisch, H.; Truong, V. X.; Barner-Kowollik, C. Nat. Comm. 2020, 11, 4193. 5. Menzel, J.P. ; Noble, B.B. ; Blinco, J.P.; Barner-Kowollik, C. Nat. Comm. 2021, 12, 1691. 6. Rodrigues, L. L; Micallef, A. S.; Pfrunder, M.; Truong, V.X.; McMurtrie, J. C.; Dargaville, T.R.; Goldmann, A. S.; Feist, F.; Barner-Kowollik, C. J. Am. Chem. Soc. 2021, 143, 7292. 7. Houck, H. A.; Blasco, E.; Du Prez, F. E.; Barner-Kowollik, C. J. Am. Chem. Soc. 2019, 141, 12329. 8. Kodura, D.; Houck, H. A.; Bloesser, F. R.; Goldmann, A. S.; Du Prez, F. E.; Frisch, H.; Barner-Kowollik, C. Chem. Sci. 2021, 12, 1302. 9. Kodura, D.; Rodrigues, L. L.; Walden, S. L.; Goldmann, A. S.; Frisch, F.; Barner-Kowollik, C. J. Am. Chem. Soc. 2022, 144, 6343-6348 10. Walden, S. L.; Rodrigues, L. L.; Alves, J.; Blinco, J. P.; Truong, V. X.; Barner-Kowollik, C. Nat. Comm. 2022, 13, 2943. 11. Thai, D. L.; Guimarães, T. R.; Chambers, L. C.; Kammerer, J. A.; Golberg, D.; Mutlu, H.; Barner-Kowollik, C. J. Am. Chem. Soc. 2023, 145, 14748.
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