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Push‐Pull Stiff‐Stilbene: Proton‐Gated Visible‐Light Photoswitching and Acid‐Catalyzed Isomerization
Author(s) -
Villarón David,
Duindam Nol,
Wezenberg Sander J.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202103052
Subject(s) - isomerization , photochemistry , protonation , photochromism , chemistry , proton , visible spectrum , gating , absorption (acoustics) , catalysis , materials science , optoelectronics , organic chemistry , physiology , ion , physics , quantum mechanics , biology , composite material
Donor‐acceptor substituted stiff‐stilbene is shown to undergo isomerization induced by visible light avoiding the need for harmful UV light. This visible‐light photoswitching is inhibited by protonation of the dimethylamino‐donor unit, disrupting the push‐pull character and thus, gating of the photochromic properties is allowed by acid/base addition. Remarkably, the addition of a mild acid also triggers fast thermal back‐isomerization, which is unprecedented for stiff‐stilbene photoswitches usually having a very high energy barrier for this process. These combined features offer unique orthogonal control over switching behavior by light and protonation, which is investigated in detail by 1 H NMR and UV/Vis spectroscopy. In addition, TD‐DFT calculations are used to gain further insight into the absorption properties. Our results will help elevating the level of control over dynamic behavior in stiff‐stilbene applications.