Unraveling ultrafast dynamics of the photoswitchable bridged dithienylethenes under structural constraints

The excited state dynamics of constrained photochromic benzodithienylethenes were addressed by considering the bridging with polyether chains (from x = 4 to 6 units) at the ortho and meta positions of the aryl group, named DTE-o x and DTE-m x , via time-resolved absorption spectroscopy supported wit...

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Published in:Physical chemistry chemical physics : PCCP 2019, Vol.21 (12), p.647-6414
Main Authors: Hamdi, Ismail, Buntinx, Guy, Poizat, Olivier, Delbaere, Stéphanie, Perrier, Aurélie, Yamashita, Rikiya, Muraoka, Ken-ichi, Takeshita, Michinori, Aloïse, Stéphane
Format: Article
Language:English
Subjects:
Aromatic compounds
Atomic energy levels
Chains
Chemical Sciences
Mathematical analysis
or physical chemistry
Spectrum analysis
Theoretical and
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Summary:The excited state dynamics of constrained photochromic benzodithienylethenes were addressed by considering the bridging with polyether chains (from x = 4 to 6 units) at the ortho and meta positions of the aryl group, named DTE-o x and DTE-m x , via time-resolved absorption spectroscopy supported with (TD)-DFT calculations. The photochromic parameters and geometrical structures of these series are discussed. A novel photocyclization pathway via a triplet state, evidenced recently (Hamdi et al. , Phys. Chem. Chem. Phys. , 2016, 18 , 28091-28100), is largely dependent on the length and the position of the polyether chain. For the first time, by comparing the two series, we revealed, for the DTE-o x series, an interconversion not only in the ground state but also between the triplet states of the anti-parallel and parallel open form conformers. Photochemistry of the bridged dithienylethene series with evidence of anti-parallel/parallel interconversion along the triplet pathway.
ISSN:1463-9076
1463-9084
DOI:10.1039/c8cp07100d