Authors: Bloch, Witold M.
Horiuchi, Shinnosuke
Holstein, Julian J.
Drechsler, Christoph
Wuttke, Axel
Hiller, Wolf
Mata, Ricardo A.
Clever, Guido H.
Title: Maximized axial helicity in a Pd2L4 cage: inverse guest size-dependent compression and mesocate isomerism
Language (ISO): en
Abstract: Helicity 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.
Subject Headings: Supramolecular chemistry
Supramolecular host
Anion binding
Issue Date: 2023-01-19
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Appears in Collections:Lehrstühle für Anorganische Chemie

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