Redox Control over Acyl Hydrazone Photoswitches

Ivica Cvrtila, Hugo Fanlo-Virgos, Gael Schaeffer, Guillermo Monreal Santiago, Sijbren Otto*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

35 Citations (Scopus)
318 Downloads (Pure)

Abstract

Photoisomerization provides a clean and efficient way of reversibly altering physical properties of chemical systems and injecting energy into them. These effects have been applied in development of systems such as photoresponsive materials, molecular motors, and photoactivated drugs. Typically, switching from more to less stable isomer(s) is performed by irradiation with UV or visible light, while the reverse process proceeds thermally or by irradiation using another wavelength. In this work we developed a method of rapid and tunable Z -> E isomerization of C = N bond in acyl hydrazones, using aromatic thiols as nucleophilic catalysts. As thiols can be oxidized into catalytically inactive disulfides, the isomerization rates can be controlled via the oxidation state of the catalyst, which, together with the UV irradiation, provides orthogonal means to control the E/Z state of the system. As a proof of this concept, we have applied this method to control the diversity of acyl hydrazone based dynamic combinatorial libraries.

Original languageEnglish
Pages (from-to)12459-12465
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number36
DOIs
Publication statusPublished - 13-Sep-2017

Keywords

  • DYNAMIC COMBINATORIAL CHEMISTRY
  • FORMING ELIMINATION-REACTIONS
  • DRIVEN MOLECULAR MOTORS
  • ORGANIC DIVALENT SULFUR
  • SYSTEMS CHEMISTRY
  • CARBINOLAMINE DEHYDRATION
  • ISOMERIZATION MECHANISM
  • INTRAMOLECULAR MOBILITY
  • THERMAL-ISOMERIZATION
  • FUNCTIONAL MATERIALS

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