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The influence of metal-complexing macrocycle size on intramolecular movement in rotaxanes

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dc.abstract.en[2]rotaxanes composed of a dibenzo-24-crown-8 wheel (DB24C8) and an axle containing two metal-complexing tetraazamacrocyclic units linked with a p-xylylene bridge, coordinating the same or different metal ions (Ni and/or Cu) are described. A symmetric di-Ni rotaxane crystallizes in the monoclinic P21/c space group with one rotaxane cation and four PF6− counterions in the asymmetric part of the unit cell. In the crystal, the cations and anions of the investigated compound form an intertwined 3D-framework with C–H⋯F and C–H⋯π intermolecular interactions. The NMR ROESY spectrum of the diamagnetic di-Ni rotaxane confirms that at room temperature slow shuttling of the DB24C8 moiety takes place along the symmetric axle. The non-symmetric rotaxane, containing 14- and 16-membered nickel(ii)-complexing macrocycles, exists in solution as an equilibrium mixture of two conformers in the ratio of ca. 1 : 7. This rotaxane behaves as a potential-controlled molecular switch: in the major isomer, the DB24C8 moiety is localized in the vicinity of the 14-membered metal-complexing macrocycle, and moves towards the 16-membered unit upon the first oxidation. Reverse translocation occurs after the subsequent oxidation of the 14-membered complex unit. In contrast, no such movements of the DB24C8 moiety were observed upon investigation of the heteronuclear [2]rotaxane, coordinating copper(ii) and nickel(ii) ions.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorWoźny, Mateusz
dc.contributor.authorWięckowska, Agnieszka
dc.contributor.authorTomczyk, Karolina
dc.contributor.authorKorybut-Daszkiewicz, Bohdan
dc.contributor.authorTrzybiński, Damian
dc.contributor.authorWoźniak, Krzysztof
dc.contributor.authorSutuła, Szymon
dc.date.accessioned2024-01-26T10:26:12Z
dc.date.available2024-01-26T10:26:12Z
dc.date.issued2019
dc.description.financeNie dotyczy
dc.description.number19
dc.description.volume48
dc.identifier.doi10.1039/C9DT00083F
dc.identifier.issn1477-9226
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/122537
dc.identifier.weblinkhttp://dx.doi.org/10.1039/C9DT00083F
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofDalton Transactions
dc.relation.pages6546-6557
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.titleThe influence of metal-complexing macrocycle size on intramolecular movement in rotaxanes
dc.typeJournalArticle
dspace.entity.typePublication