Redox Switchable Thianthrene Cavitands
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Author(s)
Bertani, Federico
Dalcanale, Enrico
Ong, Wen Jie
Swager, Timothy M
Date Issued
November 2016
Journal
Synthesis
Publisher
Thieme Publishing Group
Citation
Ong, Wen, et al. “Redox Switchable Thianthrene Cavitands.” Synthesis, vol. 49, no. 02, Nov. 2016, pp. 358–64.
Version
Original manuscript
Abstract
A redox activated vase-to-kite conformational change is reported for a new resorcinarene-based cavitand appended with four quinoxaline-fused thianthrene units. In its neutral state, the thianthrene-containing cavitand was shown by 1H NMR to adopt a closed vase conformation. Upon oxidation the electrostatic repulsion among the thianthrene radical cations promotes a kite conformation in the thianthrene-containing cavitand. The addition of acid produced a shoulder feature below 300 nm in the cavitand’s UV-Vis spectrum that we have assigned to the vase-to-kite conformation change. UV-Vis spectroelectrochemical studies of the cavitand revealed a development of a similar shoulder peak consistent with the oxidation-induced vase-to-kite conformation change. To support that the shoulder peak is diagnostic for a vase-to-kite conformation change, a model molecule constituting a single quinoxaline wall of the cavitand was synthesized and studied. As expected UV-Vis spectroelectrochemical studies of the cavitand arm did not display a shoulder peak below 300 nm. The oxidation-induced vase-to-kite conformation is further confirmed by the distinctive upfield shift in 1H chemical shift of the methine signal. Key words: redox active, thianthrene, resorcinarene cavitands, electrochemical switching, conformation change
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1055/s-0036-1588659
