Tight Xenon Confinement in a Crystalline Sandwich-like Hydrogen-Bonded Dimeric Capsule of a Cyclic Peptide
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Wiley-VCH Verlag GmbH & Co. KGaA
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Abstract
A cyclic hexapeptide with three pyridyl moieties connected to its backbone forms a hydrogen-bonded dimer, which tightly encapsulates a single xenon atom, like a pearl in its shell. The dimer imprints its shape and symmetry to the captured xenon atom, as demonstrated by Xe-129 NMR spectroscopy, single-crystal X-ray diffraction, and computational studies. The dimers self-assemble hierarchically into tubular structures to form a porous supramolecular architecture, whose cavities are filled by small molecules and gases.
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This is the peer reviewed version of the following article: A. Pizzi, H. L. Ozores, M. Calvelo, R. García-Fandiño, M. Amorín, N. Demitri, G. Terraneo, S. Bracco, A. Comotti, P. Sozzani, C. X. Bezuidenhout, P. Metrangolo, J. R. Granja, Angew. Chem. Int. Ed. 2019, 58, 14472, which has been published in final form at https://doi.org/10.1002/anie.201906599. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
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A. Pizzi, H. L. Ozores, M. Calvelo, R. García-Fandiño, M. Amorín, N. Demitri, G. Terraneo, S. Bracco, A. Comotti, P. Sozzani, C. X. Bezuidenhout, P. Metrangolo, J. R. Granja, Angew. Chem. Int. Ed. 2019, 58, 14472
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https://doi.org/10.1002/anie.201906599Sponsors
This work was supported by the Spanish Agencia Estatal de Investigación (AEI) and the ERDF (CTQ2016-78423-R), as well as by the Xunta de Galicia and the ERDF (ED431C 2017/25 and Centro singular de investigación de Galicia accreditation 2016–2019, ED431G/09). We also thank the ORFEO-CINCA network and Mineco (CTQ2016-81797-REDC). A.C. and P.S. would like to thank PRIN 2016-NAZ-0104 and PRIN 2018 (NEMO). Funding from the European Research Council for the Starting Grant ERC-2012-StG_20111012 FOLDHALO (Grant Agreement 307108) and the Proof-of-Concept Grant ERC-2017-PoC MINIRES (Grant Agreement 789815) is gratefully acknowledged. Financial support from the Italian Ministry of University and Research (MIUR) through grant “Dipartimenti di Eccellenza-2017 ”Materials For Energy“ is gratefully acknowledged. M. Negroni is greatly acknowledged for the NMR spectra. We thank the ”Centro de Supercomputación de Galicia (CESGA)“ for the use of their computational resources. R.G.-F. thanks the Ministerio de Ciencia, Innovación y Universidades for a ”Ramón y Cajal“ contract (RYC-2016-20335). M.C. thanks the Xunta de Galicia for his predoctoral contract.