Computational Design and Synthesis of a Deeply Red-Shifted and Bistable Azobenzene

David B. Konrad, Gökcen Savasci, Lars Allmendinger, Dirk Trauner, Christian Ochsenfeld, Ahmed M. Ali

Research output: Contribution to journalArticle

Abstract

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 → π∗ 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 → π∗ 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.

Original languageEnglish (US)
Pages (from-to)6538-6547
Number of pages10
JournalJournal of the American Chemical Society
Volume142
Issue number14
DOIs
StatePublished - Apr 8 2020

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Konrad, D. B., Savasci, G., Allmendinger, L., Trauner, D., Ochsenfeld, C., & Ali, A. M. (2020). Computational Design and Synthesis of a Deeply Red-Shifted and Bistable Azobenzene. Journal of the American Chemical Society, 142(14), 6538-6547. https://doi.org/10.1021/jacs.9b10430