4.6 Article

Supramolecular Alloys from Fluorinated Hybrid Tri4Di6 Imine Cages

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 33, Pages 8457-8460

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202100891

Keywords

cage compounds; crystal structures; dynamic covalent chemistry; fluorine chemistry; materials

Funding

  1. Fonds der Chemischen Industrie by a Kekule Fellowship by the North Rhine-Westphalian Academy of Sciences, Humanities and the Arts
  2. Deutsche Forschungs-gemeinschaft (DFG, German Research Foundation) [SCHM 3101/5-1]
  3. Projekt DEAL

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By carefully controlling the feed ratio, control over the outcome of the self-assembly process can be achieved to obtain highly crystalline hybrid materials of fluorinated/hydrogenated porous organic cages.
To create innovative materials, efficient control and engineering of pore sizes and their characteristics, crystallinity and stability is required. Eight hybrid Tri(4)Di(6) imine cages with a tunable degree of fluorination and one fully fluorinated Tri(4)Di(6) imine cage are investigated. Although the fluorinated and the non-fluorinated building blocks used herein differ vastly in reactivity, it was possible to gain control over the outcome of the self-assembly process, by carefully controlling the feed ratio. This represents the first hybrid material based on fluorinated/hydrogenated porous organic cages (POCs). These cages with unlimited miscibility in the solid state were obtained as highly crystalline samples after recrystallization and even showed retention of the crystal lattice, forming alloys. All mixtures and the fully fluorinated Tri(4)Di(6) imine cage were analyzed by MALDI-MS, single-crystal XRD, powder XRD and in regard to thermal stability (TGA).

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