{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:59:16Z","timestamp":1760299156836},"reference-count":54,"publisher":"Royal Society of Chemistry (RSC)","content-domain":{"domain":["rsc.org"],"crossmark-restriction":true},"short-container-title":["Faraday Discuss."],"abstract":"<p>A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH \u2248 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the <italic>cis<\/italic>-chalcone. Finally, this last species isomerizes to give the <italic>trans<\/italic>-chalcone. For the present system only the flavylium cation and the <italic>trans<\/italic>-chalcone species could be detected as being thermodynamically stable. The hemiketal and the <italic>cis<\/italic>-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1\u2009:\u20091 and 2\u2009:\u20091 host\u2009:\u2009guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10<sup>5<\/sup>\u201310<sup>8<\/sup> M<sup>\u22121<\/sup> and 10<sup>3<\/sup>\u201310<sup>4<\/sup> M<sup>\u22121<\/sup>, respectively. The 1\u2009:\u20091 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (\u224812) the flavylium cation interconverts into the deprotonated <italic>trans<\/italic>-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated <italic>trans<\/italic>-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in <italic>ca.<\/italic> 20 hours. By taking advantage of the pH-dependent kinetics of the <italic>trans<\/italic>-chalcone\/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.<\/p>","DOI":"10.1039\/c5fd00078e","type":"journal-article","created":{"date-parts":[[2015,6,9]],"date-time":"2015-06-09T14:30:55Z","timestamp":1433860255000},"page":"361-379","update-policy":"http:\/\/dx.doi.org\/10.1039\/rsc_crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes"],"prefix":"10.1039","volume":"185","author":[{"given":"Ana Marta","family":"Diniz","sequence":"first","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV)"},{"name":"REQUIMTE"},{"name":"Departamento de Qu\u00edmica"},{"name":"Faculdade de Ci\u00eancias e Tecnologia"},{"name":"Universidade Nova de Lisboa"}]},{"given":"Nuno","family":"Bas\u00edlio","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV)"},{"name":"REQUIMTE"},{"name":"Departamento de Qu\u00edmica"},{"name":"Faculdade de Ci\u00eancias e Tecnologia"},{"name":"Universidade Nova de Lisboa"}]},{"given":"Hugo","family":"Cruz","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV)"},{"name":"REQUIMTE"},{"name":"Departamento de Qu\u00edmica"},{"name":"Faculdade de Ci\u00eancias e Tecnologia"},{"name":"Universidade Nova de Lisboa"}]},{"given":"Fernando","family":"Pina","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV)"},{"name":"REQUIMTE"},{"name":"Departamento de Qu\u00edmica"},{"name":"Faculdade de Ci\u00eancias e Tecnologia"},{"name":"Universidade Nova de Lisboa"}]},{"given":"A. 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Jorge Parola (ResearcherID)","URL":"http:\/\/www.researcherid.com\/rid\/F-4048-2010","name":"identifier","group":{"name":"author_identifiers","label":"IDENTIFIERS"}},{"value":"The Royal Society of Chemistry has an exclusive publication licence for this journal","name":"copyright_licence","group":{"name":"copyright_licensing","label":"COPYRIGHT AND LICENSING"}},{"value":"Single-blind","order":2,"name":"peer_review_method","group":{"name":"peer_review_method","label":"PEER REVIEW METHOD"}},{"value":"Received 13 May 2015; Accepted 9 June 2015;  Accepted Manuscript published 9 June 2015;  Advance Article published 23 September 2015;  Version of Record published 22 December 2015","order":1,"name":"history","group":{"name":"publication_history","label":"PUBLICATION HISTORY"}}]}}