Photo-induced 6π-electrocyclisation and cycloreversion of isolated dithienylethene anions

Buntine, Jack T., Carrascosa, Eduardo, Bullock, James N., Muller, Giel, Jacovella, Ugo, Glasson, Christopher R., Vamvounis, George, and Bieske, Evan J. (2022) Photo-induced 6π-electrocyclisation and cycloreversion of isolated dithienylethene anions. Physical Chemistry Chemical Physics, 24. pp. 16628-16636.

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Abstract

The diarylethene chromophore is commonly used in light-triggered molecular switches. The chromophore undergoes reversible 6π-electrocyclisation (ring closing) and cycloreversion (ring opening) reactions upon exposure to UV and visible light, respectively, providing bidirectional photoswitching. Here, we investigate the gas-phase photoisomerisation of meta- (m) and para- (p) substituted dithienylethene carboxylate anions (DTE¯) using tandem ion mobility mass spectrometry coupled with laser excitation. The ring-closed forms of p-DTE¯ and m-DTE¯ are found to undergo cycloreversion in the gas phase with maximum responses associated with bands in the visible (λmax ≈ 600 nm) and the ultraviolet (λmax ≈ 360 nm). The ring-open p-DTE¯ isomer undergoes 6π-electrocyclisation in the ultraviolet region at wavelengths shorter than 350 nm, whereas no evidence is found for the corresponding electrocyclisation of ring-open m-DTE¯, a situation attributed to the fact that the antiparallel geometry required for electrocyclisation of m-DTE¯ is energetically disfavoured. This highlights the influence of the carboxylate substitution position on the photochemical properties of DTE molecules. We find no evidence for the formation in the gas phase of the undesirable cyclic byproduct, which causes fatigue of DTE photoswitches in solution.

Item ID: 76075
Item Type: Article (Research - C1)
ISSN: 1463-9084
Copyright Information: © the Owner Societies 2022
Funders: Australian Research Council (ARC)
Projects and Grants: ARC DP150101427, ARC DP160100474, ARC DP1095404
Research Data: https://www.rsc.org/suppdata/d2/cp/d2cp01240e/d2cp01240e1.pdf
Date Deposited: 20 Sep 2022 00:13
FoR Codes: 34 CHEMICAL SCIENCES > 3403 Macromolecular and materials chemistry > 340304 Optical properties of materials @ 100%
SEO Codes: 28 EXPANDING KNOWLEDGE > 2801 Expanding knowledge > 280105 Expanding knowledge in the chemical sciences @ 50%
24 MANUFACTURING > 2409 Industrial chemicals and related products > 240904 Fine chemicals @ 50%
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