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

doi:10.1021/acs.cgd.8b00630

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

Chemistry and Nanoscience

Research output: Contribution to journal › Article › peer-review

29 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 language	American English
Pages (from-to)	4160-4166
Number of pages	7
Journal	Crystal Growth and Design
Volume	18
Issue number	7
DOIs	https://doi.org/10.1021/acs.cgd.8b00630 https://doi.org/10.1021/acs.cgd.8b00630
State	Published - 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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Johnson, J., Braunecker, W., Hurst, K., Owczarczyk, Z., Sellinger, A., Keuhlen, A., Ray, K., Martinez, M., & Marius, N. (2018). Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks. Crystal Growth and Design, 18(7), 4160-4166. https://doi.org/10.1021/acs.cgd.8b00630, https://doi.org/10.1021/acs.cgd.8b00630

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Johnson, J , Braunecker, W , Hurst, K , Owczarczyk, Z, Sellinger, A, Keuhlen, A, Ray, K, Martinez, M & Marius, N 2018, 'Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks', Crystal Growth and Design, vol. 18, no. 7, pp. 4160-4166. https://doi.org/10.1021/acs.cgd.8b00630, https://doi.org/10.1021/acs.cgd.8b00630

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AU - Johnson, Justin

AU - Braunecker, Wade

AU - Hurst, Katherine

AU - Owczarczyk, Zbyslaw

AU - Sellinger, Alan

AU - Keuhlen, Amy

AU - Ray, Keith

AU - Martinez, Madison

AU - Marius, Noemie

PY - 2018/7/5

Y1 - 2018/7/5

N2 - 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.

AB - 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.

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

Abstract

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Keywords

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