Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching
Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature o...
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Veröffentlicht in: | Angewandte Chemie International Edition 2018-07, Vol.57 (27), p.8063-8068 |
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Sprache: | eng |
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Zusammenfassung: | Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.
DASAs (dis)solved: The actinic step of the photoswitching mechanism of donor–acceptor Stenhouse adducts is similar across a range of solvents from apolar aprotic to polar protic. The energies and absorption spectra of photoswitching intermediates, however, change with solvent polarity and the protic nature of the solvent, affecting the overall photoswitching behavior. |
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ISSN: | 1433-7851 1521-3773 |
DOI: | 10.1002/anie.201803058 |