Interplay of Stereochemistry and Charge Governs Guest Binding in Flexible Zn II 4 L 4 Cages.

Autor:	Xue W; Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu 610064, China.; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany.; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Benchimol E; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany., Walther A; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany., Ouyang N; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Holstein JJ; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany., Ronson TK; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Openy J; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany., Zhou Y; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Wu K; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K., Chowdhury R; Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE, U.K., Clever GH; Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, Dortmund 44227, Germany., Nitschke JR; Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, U.K.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2024 Nov 27; Vol. 146 (47), pp. 32730-32737. Date of Electronic Publication: 2024 Nov 14.
DOI:	10.1021/jacs.4c12320
Abstrakt:	Here, we report the synthesis of a family of chiral Zn II 4 L 4 tetrahedral cages by subcomponent self-assembly. These cages contain a flexible trialdehyde subcomponent that allows them to adopt stereochemically distinct configurations. The incorporation of enantiopure 1-phenylethylamine produced Δ 4 and Λ 4 enantiopure cages, in contrast to the racemates that resulted from the incorporation of achiral 4-methoxyaniline. The stereochemistry of these Zn II 4 L 4 tetrahedra was characterized by X-ray crystallography and chiroptical spectroscopy. Upon binding the enantiopure natural product podocarpic acid, the Zn II stereocenters of the enantiopure Δ 4 -Zn II 4 L 4 cage retained their Δ handedness. In contrast, the metal stereocenters of the enantiomeric Λ 4 -Zn II 4 L 4 cage underwent inversion to a Δ configuration upon encapsulation of the same guest. Insights gained about the stereochemical communication between host and guest enabled the design of a process for acid/base-responsive guest uptake and release, which could be followed by chiroptical spectroscopy.
Databáze:	MEDLINE
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