Action Plots in Action: In-Depth Insights into Photochemical Reactivity
| Autor: | Ishrath M. Irshadeen, Hendrik Frisch, Vinh X. Truong, Martin Wegener, Sarah L. Walden, James P. Blinco, Christopher Barner-Kowollik |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
Nitrile
Absorption spectroscopy 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry 01 natural sciences Biochemistry Catalysis Spectral line 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry chemistry Covalent bond Molecule Reactivity (chemistry) 0210 nano-technology Photoinitiator Excitation |
| Zdroj: | Journal of the American Chemical Society. 143(50) |
| ISSN: | 1520-5126 |
| Popis: | Predicting wavelength-dependent photochemical reactivity is challenging. Herein, we revive the well-established tool of measuring action spectra and adapt the technique to map wavelength-resolved covalent bond formation and cleavage in what we term "photochemical action plots". Underpinned by tunable lasers, which allow excitation of molecules with near-perfect wavelength precision, the photoinduced reactivity of several reaction classes have been mapped in detail. These include photoinduced cycloadditions and bond formation based on photochemically generated o-quinodimethanes and 1,3-dipoles such as nitrile imines as well as radical photoinitiator cleavage. Organized by reaction class, these data demonstrate that UV/vis spectra fail to act as a predictor for photochemical reactivity at a given wavelength in most of the examined reactions, with the photochemical reactivity being strongly red shifted in comparison to the absorption spectrum. We provide an encompassing perspective of the power of photochemical action plots for bond-forming reactions and their emerging applications in the design of wavelength-selective photoresists and photoresponsive soft-matter materials. |
| Databáze: | OpenAIRE |
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