Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 14, Pages 6538-6547Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b10430
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Funding
- Georg Forster Research Fellowship (Alexander von Humboldt Foundation)
- Innovative Training Network Computational Spectroscopy in Natural Sciences and Engineering (ITN-COSINE)
- European Union [754388]
- LMU Munich's Institutional Strategy LMUexcellent within the framework of the German Excellence Initiative [ZUK22]
- [SFB749]
- Marie Curie Actions (MSCA) [754388] Funding Source: Marie Curie Actions (MSCA)
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We computationally dissected the electronic and geometrical influences of ortho-chlorinated azobenzenes on their photophysical properties. X-ray analysis provided the insight that trans-tetra-ortho-chloro azobenzene is conformationally flexible and thus subject to molecular motions. This allows the photoswitch to adopt a range of red-shifted geometries, which account for the extended n -> pi* band tails. On the basis of our results, we designed the di-ortho-fluoro di-ortho-chloro (dfdc) azobenzene and provided computational evidence for the superiority of this substitution pattern to tetra-ortho-chloro azobenzene. Thereafter, we synthesized dfdc azobenzene by ortho-chlorination via 2-fold C-H activation and experimentally confirmed its structural and photophysical properties through UV-vis, NMR, and X-ray analyses. The advantages include near-bistable isomers and an increased separation of the n -> pi* bands between the trans- and cis-conformations, which allows for the generation of unusually high levels of the cis-isomer by irradiation with green/yellow light as well as red light within the biooptical window.
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