Maximized axial helicity in a Pd2L4 cage: inverse guest size-dependent compression and mesocate isomerism

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dc.contributor.authorBloch, Witold M.
dc.contributor.authorHoriuchi, Shinnosuke
dc.contributor.authorHolstein, Julian J.
dc.contributor.authorDrechsler, Christoph
dc.contributor.authorWuttke, Axel
dc.contributor.authorHiller, Wolf
dc.contributor.authorMata, Ricardo A.
dc.contributor.authorClever, Guido H.
dc.date.accessioned2023-02-01T10:12:01Z
dc.date.available2023-02-01T10:12:01Z
dc.date.issued2023-01-19
dc.description.abstractHelicity is an archetypal structural motif of many biological systems and provides a basis for molecular recognition in DNA. Whilst artificial supramolecular hosts are often helical, the relationship between helicity and guest encapsulation is not well understood. We report a detailed study on a significantly coiled-up Pd2L4 metallohelicate with an unusually wide azimuthal angle (∼176°). Through a combination of NMR spectroscopy, single-crystal X-ray diffraction, trapped ion mobility mass spectrometry and isothermal titration calorimetry we show that the coiled-up cage exhibits extremely tight anion binding (K of up to 106 M−1) by virtue of a pronounced oblate/prolate cavity expansion, whereby the Pd–Pd separation decreases for mono-anionic guests of increasing size. Electronic structure calculations point toward strong dispersion forces contributing to these host–guest interactions. In the absence of a suitable guest, the helical cage exists in equilibrium with a well-defined mesocate isomer that possesses a distinct cavity environment afforded by a doubled Pd–Pd separation distance.en
dc.identifier.urihttp://hdl.handle.net/2003/41220
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-23064
dc.language.isoende
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/
dc.subjectSupramolecular chemistryen
dc.subjectHelicityen
dc.subjectSupramolecular hosten
dc.subjectMetallohelicateen
dc.subjectAnion bindingen
dc.subject.ddc540
dc.titleMaximized axial helicity in a Pd2L4 cage: inverse guest size-dependent compression and mesocate isomerismen
dc.typeTextde
dc.type.publicationtypearticlede
dcterms.accessRightsopen access
eldorado.openaire.projectidentifierinfo:eu-repo/grantAgreement/EC/H2020/683083/EU/Reactivity and Assembly of Multifunctional, Stimuli-responsive Encapsulation Structures/RAMSESde
eldorado.secondarypublicationtruede
eldorado.secondarypublication.primarycitationBloch, Witold M., Shinnosuke Horiuchi, Julian J. Holstein, Christoph Drechsler, Axel Wuttke, Wolf Hiller, Ricardo A. Mata, und Guido H. Clever. „Maximized axial helicity in a Pd2L4 cage: inverse guest size-dependent compression and mesocate isomerism“. Chemical Science, 2023. https://doi.org/10.1039/d2sc06629g.de
eldorado.secondarypublication.primaryidentifierDOI: https://doi.org/10.1039/D2SC06629Gde

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