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

Buntine, Jack, Carrascosa, Eduardo, Bull, James N. ORCID: https://orcid.org/0000-0003-0953-1716, 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 (27). pp. 16628-16636. ISSN 1463-9076

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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 (λ max ≈ 600 nm) and the ultraviolet (λ max ≈ 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 Type: Article
Additional Information: Funding Information: This research was funded through the Australian Research Council Discovery Project scheme (DP150101427 and DP160100474). G. V. thanks the Australian Research Council for the Australian Research Fellowship (DP1095404) support. J. T. B. acknowledges support by The University of Melbourne through a Melbourne Research Scholarship and an Australian Research Training Program Scholarship (RTP). G. M. acknowledges the Australian Government's support through an Australian Postgraduate Award (APA) and an Australian Research Training Program Scholarship. E. C. acknowledges support by the Austrian Science Fund (FWF) through a Schrödinger Fellowship (No. J4013-N36). U. J. acknowledges support by the Swiss National Science Foundation (P2EZP2_ 178429).
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 28 Jun 2022 09:30
Last Modified: 21 Jul 2022 08:31
URI: https://ueaeprints.uea.ac.uk/id/eprint/85824
DOI: 10.1039/D2CP01240E

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