Concentration-Dependent Self-Assembly of an Unusually Large Hexameric Hydrogen-Bonded Molecular Cage

Severin Merget; Lorenzo Catti; Shani Zev; Dan T. Major; Nils Trapp; Konrad Tiefenbacher

doi:10.1002/chem.202005046

Concentration-Dependent Self-Assembly of an Unusually Large Hexameric Hydrogen-Bonded Molecular Cage

Severin Merget, Lorenzo Catti, Shani Zev, Dan T. Major, Nils Trapp, Konrad Tiefenbacher

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The sizes of available self-assembled hydrogen-bond-based supramolecular capsules and cages are rather limited. The largest systems have volumes of approximately 1400–2300 Å³. Herein, we report a large, hexameric cage based on intermolecular amide–amide dimerization. The unusual structure with openings, reminiscent of covalently linked cages, is held together by 24 hydrogen bonds. With a diameter of 2.3 nm and a cavity volume of ∼2800 Å³, the assembly is larger than any previously known capsule/cage structure relying exclusively on hydrogen bonds. The self-assembly process in chlorinated, organic solvents was found to be strongly concentration dependent, with the monomeric form prevailing at low concentrations. Additionally, the formation of host–guest complexes with fullerenes (C₆₀ and C₇₀) was observed.

Original language	English
Pages (from-to)	4447-4453
Number of pages	7
Journal	Chemistry - A European Journal
Volume	27
Issue number	13
DOIs	https://doi.org/10.1002/chem.202005046
State	Published - 1 Mar 2021

Bibliographical note

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Funding

This work was supported by funding from the European Research Council Horizon 2020 Programme (ERC Starting Grant 714620—TERPENECAT) and the Swiss National Science Foundation as part of the NCCR Molecular Systems Engineering. We thank P.D. Dr. Daniel Häussinger and Fabian Bissegger for assistance with the DOSY NMR and VT NMR measurements as well as Dr. Michael Pfeffer for HRMS analysis. L.C. thanks the Japan Society for the Promotion of Science and the Alexander von Humboldt Foundation for a postdoctoral fellowship. This work was also supported by a grant from the Israeli Science Foundation (grant 1683/18; D.T.M.).

Funders	Funder number
European Research Council Horizon 2020 Programme
NCCR Molecular Systems Engineering
Alexander von Humboldt-Stiftung
Horizon 2020 Framework Programme	714620
European Commission
Japan Society for the Promotion of Science
Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
Israel Science Foundation	1683/18

Keywords

amides
fullerenes
host–guest complexes
self-assembly
supramolecular chemistry

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10.1002/chem.202005046

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Concentration-Dependent Self-Assembly of an Unusually Large Hexameric Hydrogen-Bonded Molecular Cage

Abstract

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Keywords

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