Autor(en): | Bloch, Witold M. Horiuchi, Shinnosuke Holstein, Julian J. Drechsler, Christoph Wuttke, Axel Hiller, Wolf Mata, Ricardo A. Clever, Guido H. |
Titel: | Maximized axial helicity in a Pd2L4 cage: inverse guest size-dependent compression and mesocate isomerism |
Sprache (ISO): | en |
Zusammenfassung: | 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. |
Schlagwörter: | Supramolecular chemistry Helicity Supramolecular host Metallohelicate Anion binding |
URI: | http://hdl.handle.net/2003/41220 http://dx.doi.org/10.17877/DE290R-23064 |
Erscheinungsdatum: | 2023-01-19 |
Rechte (Link): | https://creativecommons.org/licenses/by-nc/3.0/ |
Enthalten in den Sammlungen: | Lehrstühle für Anorganische Chemie |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | |
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Bloch_Horiuchi_Clever_Chem.Sci..pdf | 923.75 kB | Adobe PDF | Öffnen/Anzeigen |
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