Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF wi...

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Bibliographic Details
Published in:Crystal growth & design 2018-07, Vol.18 (7), p.4160-4166
Main Authors: Braunecker, Wade A, Hurst, Katherine E, Ray, Keith G, Owczarczyk, Zbyslaw R, Martinez, Madison B, Leick, Noemi, Keuhlen, Amy, Sellinger, Alan, Johnson, Justin C
Format: Article
Language:English
Subjects:
crystal
fluorination
frameworks
gas storage
MATERIALS SCIENCE
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Summary:A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer–Emmet–Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ∼37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (∼1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features in FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.
ISSN:1528-7483
1528-7505
DOI:10.1021/acs.cgd.8b00630