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Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet‐Oxygen Production and Storage
Author(s) -
Ziani Zakaria,
Loiseau Frédérique,
Log Elise,
BoggioPasqua Martial,
Philouze Christian,
Cobo Saioa,
Royal Guy
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.202103003
Subject(s) - triphenylamine , isomerization , photochemistry , photochromism , singlet oxygen , quantum yield , chemistry , cyclic voltammetry , singlet state , oxygen , absorption (acoustics) , electron donor , acceptor , yield (engineering) , electrochemistry , fluorescence , materials science , excited state , catalysis , organic chemistry , electrode , atomic physics , physics , quantum mechanics , composite material , condensed matter physics , metallurgy
A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methylpyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry, and its properties were rationalized by theoretical calculations. The incorporation of both electron‐donor and ‐withdrawing groups at the photochromic center allows i) an efficient photo‐isomerization of the system when illuminated at low energy (quantum yield: Φ c‐o =13.3 % at λ ex =660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature, and iii) the storage and production of singlet oxygen. The photo‐isomerization mechanism was also investigated by spin‐flip TD‐DFT (SF‐TD‐DFT) calculations.