pH-Induced Orthogonal Photoresponse of <i>trans</i>-Chalcone Isomers and Related Compounds in Equilibria

Abstract

Photoresponsive molecular devices can be a valuable tool to promote chemical changes in response to multiple signals, such as photons and pH, to deliver drugs or to detect physiological conditions in vivo. For example, trans-chalcones (Ct) from 4′-hydroxyflavylium (F1) and 7-hydroxyflavylium (F2) can undergo cis-trans isomerization by photoreaction into many different structures. The isomerization takes place at a slow rate in response to pH change; however, it can be done in seconds by photoreaction. In the investigation, as confirming the previous reports, 3-(2-hydroxy-phenyl)-1-(4-hydroxy-phenyl)-propenone, the trans-chalcone (CtF1) from F1, produces flavylium ions in pH = 1–4.5. Then, we further discovered that the flavylium quickly releases protons to yield the corresponding quinoidal base (A) in a solution of pH = 5.2 during irradiation with 350 nm. Meanwhile, the photolysis of 3-(2,4-dihydroxy-phenyl)-1-phenyl-propenone, the trans-chalcone (CtF2) from F2 at pH = 5.6, induces photoacid behavior by losing a proton from the trans-chalcone to generate Ct2−. The different outcomes of these nearly colorless chalcones under similar pH conditions and with the same photochemical conditions can be useful when yielding colored AH+, A, or Ct2− in a mildly acidic pH environment with temporal and spatial control using photochemical means.

Keywords

• <i>trans</i>-chalcone
• <i>cis-trans</i> isomerization
• photoacid
• flavylium ion