Dissecting Porosity in Molecular Crystals

Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics

Mohamed I. Hashim, Ha T.M. Le, Teng Hao Chen, Yu Sheng Chen, Olafs Daugulis, Chia Wei Hsu, Allan J. Jacobson, Kaveevivitchai Watchareeya, Xiao Liang, Tatyana Makarenko, Ognjen Miljanić, Ilja Popovs, Hung Vu Tran, Xiqu Wang, Chia Hua Wu, Judy I. Wu

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Porous molecular crystals are an emerging class of porous materials that is unique in being built from discrete molecules rather than being polymeric in nature. In this study, we examined the effects of molecular structure of the precursors on the formation of porous solid-state structures with a series of 16 rigid aromatics. The majority of these precursors possess pyrazole groups capable of hydrogen bonding, as well as electron-rich aromatics and electron-poor tetrafluorobenzene rings. These precursors were prepared using a combination of Pd- and Cu-catalyzed cross-couplings, careful manipulations of protecting groups on the nitrogen atoms, and solvothermal syntheses. Our study varied the geometry and dimensions of precursors, as well as the presence of groups capable of hydrogen bonding and [π···π] stacking. Thirteen derivatives were crystallographically characterized, and four of them were found to be porous with surface areas between 283 and 1821 m2 g-1. Common to these four porous structures were (a) rigid trigonal geometry, (b) [π···π] stacking of electron-poor tetrafluorobenzenes with electron-rich pyrazoles or tetrazoles, and (c) hydrogen bonding between the terminal heteroaromatic rings.

Original languageEnglish
Pages (from-to)6014-6026
Number of pages13
JournalJournal of the American Chemical Society
Volume140
Issue number18
DOIs
Publication statusPublished - 2018 May 9

Fingerprint

Molecular crystals
Porosity
Hydrogen Bonding
Hydrogen bonds
Electrons
Geometry
Tetrazoles
Pyrazoles
Molecular Structure
Molecular structure
Porous materials
Nitrogen
Derivatives
Atoms
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hashim, Mohamed I. ; Le, Ha T.M. ; Chen, Teng Hao ; Chen, Yu Sheng ; Daugulis, Olafs ; Hsu, Chia Wei ; Jacobson, Allan J. ; Watchareeya, Kaveevivitchai ; Liang, Xiao ; Makarenko, Tatyana ; Miljanić, Ognjen ; Popovs, Ilja ; Tran, Hung Vu ; Wang, Xiqu ; Wu, Chia Hua ; Wu, Judy I. / Dissecting Porosity in Molecular Crystals : Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 18. pp. 6014-6026.
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abstract = "Porous molecular crystals are an emerging class of porous materials that is unique in being built from discrete molecules rather than being polymeric in nature. In this study, we examined the effects of molecular structure of the precursors on the formation of porous solid-state structures with a series of 16 rigid aromatics. The majority of these precursors possess pyrazole groups capable of hydrogen bonding, as well as electron-rich aromatics and electron-poor tetrafluorobenzene rings. These precursors were prepared using a combination of Pd- and Cu-catalyzed cross-couplings, careful manipulations of protecting groups on the nitrogen atoms, and solvothermal syntheses. Our study varied the geometry and dimensions of precursors, as well as the presence of groups capable of hydrogen bonding and [π···π] stacking. Thirteen derivatives were crystallographically characterized, and four of them were found to be porous with surface areas between 283 and 1821 m2 g-1. Common to these four porous structures were (a) rigid trigonal geometry, (b) [π···π] stacking of electron-poor tetrafluorobenzenes with electron-rich pyrazoles or tetrazoles, and (c) hydrogen bonding between the terminal heteroaromatic rings.",
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Hashim, MI, Le, HTM, Chen, TH, Chen, YS, Daugulis, O, Hsu, CW, Jacobson, AJ, Watchareeya, K, Liang, X, Makarenko, T, Miljanić, O, Popovs, I, Tran, HV, Wang, X, Wu, CH & Wu, JI 2018, 'Dissecting Porosity in Molecular Crystals: Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics', Journal of the American Chemical Society, vol. 140, no. 18, pp. 6014-6026. https://doi.org/10.1021/jacs.8b02869

Dissecting Porosity in Molecular Crystals : Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics. / Hashim, Mohamed I.; Le, Ha T.M.; Chen, Teng Hao; Chen, Yu Sheng; Daugulis, Olafs; Hsu, Chia Wei; Jacobson, Allan J.; Watchareeya, Kaveevivitchai; Liang, Xiao; Makarenko, Tatyana; Miljanić, Ognjen; Popovs, Ilja; Tran, Hung Vu; Wang, Xiqu; Wu, Chia Hua; Wu, Judy I.

In: Journal of the American Chemical Society, Vol. 140, No. 18, 09.05.2018, p. 6014-6026.

Research output: Contribution to journalArticle

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T2 - Influence of Geometry, Hydrogen Bonding, and [π···π] Stacking on the Solid-State Packing of Fluorinated Aromatics

AU - Hashim, Mohamed I.

AU - Le, Ha T.M.

AU - Chen, Teng Hao

AU - Chen, Yu Sheng

AU - Daugulis, Olafs

AU - Hsu, Chia Wei

AU - Jacobson, Allan J.

AU - Watchareeya, Kaveevivitchai

AU - Liang, Xiao

AU - Makarenko, Tatyana

AU - Miljanić, Ognjen

AU - Popovs, Ilja

AU - Tran, Hung Vu

AU - Wang, Xiqu

AU - Wu, Chia Hua

AU - Wu, Judy I.

PY - 2018/5/9

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N2 - Porous molecular crystals are an emerging class of porous materials that is unique in being built from discrete molecules rather than being polymeric in nature. In this study, we examined the effects of molecular structure of the precursors on the formation of porous solid-state structures with a series of 16 rigid aromatics. The majority of these precursors possess pyrazole groups capable of hydrogen bonding, as well as electron-rich aromatics and electron-poor tetrafluorobenzene rings. These precursors were prepared using a combination of Pd- and Cu-catalyzed cross-couplings, careful manipulations of protecting groups on the nitrogen atoms, and solvothermal syntheses. Our study varied the geometry and dimensions of precursors, as well as the presence of groups capable of hydrogen bonding and [π···π] stacking. Thirteen derivatives were crystallographically characterized, and four of them were found to be porous with surface areas between 283 and 1821 m2 g-1. Common to these four porous structures were (a) rigid trigonal geometry, (b) [π···π] stacking of electron-poor tetrafluorobenzenes with electron-rich pyrazoles or tetrazoles, and (c) hydrogen bonding between the terminal heteroaromatic rings.

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