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In this work, a study focused on the kinetics of a water\u2010soluble host\u2010guest system based on cucurbit[8]uril and two dithienylethene (DTE) photoswitches is reported. It is shown that for the DTE guest comprising two anionic sulfonate side arms appended to pyridinium moieties, the formation\/dissociation of the pseudorotaxane structures is slowed down by more than 100000\u2010fold with respect to its bipyridinium analogue. The decrease in ingression rate leads to the emergence of a competitive metastable product with the open DTE isomer that has an important influence in the overall binding kinetics. Moreover, the host\u2010guest dissociation kinetics is demonstrated to be approximately 100\u2010fold slower for the closed DTE isomer (t<jats:sub>1\/2<\/jats:sub>=107\u2005h vs. t<jats:sub>1\/2<\/jats:sub>=1.2\u2005h for the open isomer) allowing control over the dissociation rate with light.<\/jats:p>","DOI":"10.1002\/chem.202100974","type":"journal-article","created":{"date-parts":[[2021,4,28]],"date-time":"2021-04-28T05:37:45Z","timestamp":1619588265000},"page":"9550-9555","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Photoresponsive Binding Dynamics in High\u2010Affinity Cucurbit[8]uril\u2010Dithienylethene Host\u2010Guest Complexes"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9184-4182","authenticated-orcid":false,"given":"Miriam","family":"Cola\u00e7o","sequence":"first","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV) Rede de Qu\u00edmica e Tecnologia (REQUIMTE) Departamento de Qu\u00edmica Faculdade de Ci\u00eancias e Tecnologia Universidade NOVA de Lisboa  2829-516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0387-5411","authenticated-orcid":false,"given":"Patr\u00edcia","family":"M\u00e1ximo","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV) Rede de Qu\u00edmica e Tecnologia (REQUIMTE) Departamento de Qu\u00edmica Faculdade de Ci\u00eancias e Tecnologia Universidade NOVA de Lisboa  2829-516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1333-9076","authenticated-orcid":false,"given":"A.","family":"Jorge Parola","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV) Rede de Qu\u00edmica e Tecnologia (REQUIMTE) Departamento de Qu\u00edmica Faculdade de Ci\u00eancias e Tecnologia Universidade NOVA de Lisboa  2829-516 Caparica Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0121-3695","authenticated-orcid":false,"given":"Nuno","family":"Bas\u00edlio","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio Associado para a Qu\u00edmica Verde (LAQV) Rede de Qu\u00edmica e Tecnologia (REQUIMTE) Departamento de Qu\u00edmica Faculdade de Ci\u00eancias e Tecnologia Universidade NOVA de Lisboa  2829-516 Caparica Portugal"}]}],"member":"311","published-online":{"date-parts":[[2021,5,29]]},"reference":[{"doi-asserted-by":"publisher","key":"e_1_2_6_1_1","DOI":"10.1002\/9780470661345"},{"doi-asserted-by":"publisher","key":"e_1_2_6_2_1","DOI":"10.1073\/pnas.072065599"},{"doi-asserted-by":"publisher","key":"e_1_2_6_3_1","DOI":"10.1002\/anie.201409399"},{"doi-asserted-by":"publisher","key":"e_1_2_6_3_2","DOI":"10.1002\/ange.201409399"},{"doi-asserted-by":"publisher","key":"e_1_2_6_4_1","DOI":"10.1039\/C3CS60352K"},{"doi-asserted-by":"publisher","key":"e_1_2_6_5_1","DOI":"10.1039\/C7CS00246G"},{"doi-asserted-by":"publisher","key":"e_1_2_6_6_1","DOI":"10.1039\/C7CS00121E"},{"doi-asserted-by":"publisher","key":"e_1_2_6_7_1","DOI":"10.1021\/acs.chemrev.9b00291"},{"doi-asserted-by":"publisher","key":"e_1_2_6_8_1","DOI":"10.1039\/C7CS00068E"},{"doi-asserted-by":"publisher","key":"e_1_2_6_9_1","DOI":"10.1016\/j.chempr.2020.07.009"},{"doi-asserted-by":"publisher","key":"e_1_2_6_10_1","DOI":"10.1021\/acs.chemrev.5b00341"},{"doi-asserted-by":"publisher","key":"e_1_2_6_11_1","DOI":"10.1039\/C4CS00273C"},{"doi-asserted-by":"publisher","key":"e_1_2_6_12_1","DOI":"10.1039\/C1RA00768H"},{"doi-asserted-by":"publisher","key":"e_1_2_6_13_1","DOI":"10.1039\/C7CS00011A"},{"doi-asserted-by":"publisher","key":"e_1_2_6_14_1","DOI":"10.1039\/C5CS00631G"},{"doi-asserted-by":"publisher","key":"e_1_2_6_15_1","DOI":"10.1021\/ar5001204"},{"doi-asserted-by":"publisher","key":"e_1_2_6_16_1","DOI":"10.1021\/ol901237p"},{"doi-asserted-by":"publisher","key":"e_1_2_6_17_1","DOI":"10.1021\/ja063390j"},{"doi-asserted-by":"publisher","key":"e_1_2_6_18_1","DOI":"10.1021\/ol3021989"},{"doi-asserted-by":"publisher","key":"e_1_2_6_19_1","DOI":"10.1021\/jacs.9b09751"},{"doi-asserted-by":"publisher","key":"e_1_2_6_20_1","DOI":"10.1021\/ja404797y"},{"doi-asserted-by":"publisher","key":"e_1_2_6_21_1","DOI":"10.1021\/jacs.7b04821"},{"doi-asserted-by":"publisher","key":"e_1_2_6_22_1","DOI":"10.1021\/jp500603g"},{"doi-asserted-by":"publisher","key":"e_1_2_6_23_1","DOI":"10.1039\/C5FD00095E"},{"doi-asserted-by":"publisher","key":"e_1_2_6_24_1","DOI":"10.1021\/ja209266x"},{"doi-asserted-by":"publisher","key":"e_1_2_6_25_1","DOI":"10.1021\/jacs.9b03691"},{"key":"e_1_2_6_26_1","first-page":"1","author":"Masson E.","year":"2018","journal-title":"Isr. 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