Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype

Grosso‐Giordano, Nicolás A.; Schroeder, Christian; Xu, Le; Solovyov, Andrew; Small, David W.; Koller, Hubert; Zones, Stacey I.; Katz, Alexander

doi:10.1002/ange.202100166

Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype

Journal Article · Thu Mar 18 00:00:00 EDT 2021 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202100166· OSTI ID:1786035

^[1]; ^[2]; ^[1]; Solovyov, Andrew ^[1]; Small, David W. ^[3]; ^[2]; Zones, Stacey I. ^[4]; ^[1]

Department of Chemical and Biomolecular Engineering University of California, Berkeley Berkeley CA 94720 USA
Institut für Physikalische Chemie Westfälische Wilhelms-Universität Münster Münster Germany, Center for Soft Nanoscience Univeristy of Münster Busso-Peus-Straße 10 48149 Münster Germany
Molecular Graphics and Computation Facility College of Chemistry University of California, Berkeley Berkeley CA 94720 USA
Chevron Energy Technology Company Richmond CA 94804 USA

Abstract

We investigate the interaction between a molecule and a pore mouth—a critical step in adsorption processes—by characterizing the conformation of a macrocyclic calix[4]arene‐Ti ^IV complex, which is grafted on the external surface of a zeotype (*‐SVY). X‐ray absorption and ¹³ C{ ¹ H} CPMAS NMR spectroscopies independently detect a unique conformation of this complex when it is grafted at crystallographically equivalent locations that lie at the interface of 7 Å hemispherical microporous cavities and the external surface. Electronic structure calculations support the presence of this unique conformation, and suggest that it is brought about by a specific orientation of the macrocycle that maximizes non‐covalent interactions between calix[4]arene upper‐rim tert ‐butyl substituents and the microporous‐cavity walls. Our comparative study provides a rare “snapshot” of a molecule partially confined at a pore mouth, an essential intermediate for adsorption into micropores, and demonstrates how surrounding environment controls this confinement in a sensitive fashion.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-05ER15696; AC02-76SF00515

OSTI ID:: 1786035

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 18 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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