Accessible Requires Authentication Published by De Gruyter October 25, 2019

A pseudorotaxane formed from a cucurbit[7]uril wheel and a bioinspired molecular axle with pH, light and redox-responsive properties

André Seco, Ana Marta Diniz, João Sarrato, Henrique Mourão, Hugo Cruz, A. Jorge Parola and Nuno Basílio

Abstract

A pH-, light- and redox-responsive flavylium-bipyridinium molecular dyad (bioinspired in natural anthocyanins) was synthesized and employed to devise a pseudorotaxane with the macrocycle cucurbit[7]uril (CB7) in aqueous solution. The inclusion complex was characterized by UV-Vis absorption, fluorescence emission, NMR and electrochemical techniques which demonstrate formation of a stable binary complex between the dyad and CB7 both under acidic and neutral conditions. It is noteworthy that the flavylium-bipyridinium tricationic dyad is only stable in highly acidic media, undergoing a reversible hydration reaction at slightly acidic or neutral pH to give a trans-chalcone-bipyridinium dication. 1H NMR experiments showed that in this last species the CB7 binds to the bipyridinium unit while in the tricationic species the macrocycle is positioned between the flavylium and the bipyridinium moieties. The different location of the CB7 wheel in the two dyad states allows control of the shuttling movement using light and pH stimuli that trigger the interconversion between these two species.

Funding source: H2020-MSCA-RISE-2016

Award Identifier / Grant number: 734834

Funding statement: This work was supported by LAQV-REQUIMTE, which is financed by the Portuguese FCT/MCTES (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 (POCI-01-0145-FEDER-007265). FCT/MCTES is also acknowledged for supporting the National Portuguese NMR Network (RECI/BBB-BQB/0230/2012), projects PTDC/QUI-COL/32351/2017, PTDC/QUI-QFI/30951/2017 and CEECIND/00466/2017 (N.B.) (Funder Id: http://dx.doi.org/10.13039/501100001871). EC is acknowledged for the INFUSION project grant no. 734834 under H2020-MSCA-RISE-2016 (Funder Id: http://dx.doi.org/10.13039/100010665). H.C. acknowledges postdoctoral grant SFRH/BPD/102705/2014.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/pac-2019-0225).

Published Online: 2019-10-25
Published in Print: 2020-02-25

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