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

Justin Johnson, Wade Braunecker, Katherine Hurst, Zbyslaw Owczarczyk, Alan Sellinger, Amy Keuhlen, Keith Ray, Madison Martinez, Noemie Marius

Research output: Contribution to journalArticlepeer-review

26 Scopus Citations

Abstract

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.

Original languageAmerican English
Pages (from-to)4160-4166
Number of pages7
JournalCrystal Growth and Design
Volume18
Issue number7
DOIs
StatePublished - 5 Jul 2018

Bibliographical note

Publisher Copyright:
© Copyright 2018 American Chemical Society.

NREL Publication Number

  • NREL/JA-5900-70871

Keywords

  • crystal
  • fluorination
  • frameworks
  • gas storage

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