Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology

Pravas Deria, Diego A. Gómez-Gualdrón, Wojciech Bury, Herbert T. Schaef, Timothy C. Wang, Praveen K. Thallapally, Amy A. Sarjeant, Randall Q. Snurr, Joseph T Hupp, Omar K. Farha

Research output: Contribution to journalArticle

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Abstract

"Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) 虠 "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp 虠 op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.

Original languageEnglish
Pages (from-to)13183-13190
Number of pages8
JournalJournal of the American Chemical Society
Volume137
Issue number40
DOIs
Publication statusPublished - Oct 14 2015

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Zirconium
Propane
Respiration
Metals
Topology
Water
Sorption
Molecular modeling
Pyrene
Porphyrins
Gases
Discrete Fourier transforms
X ray powder diffraction
Conformations
X-Ray Diffraction
Powders
Crystals
Pressure

ASJC Scopus subject areas

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

Cite this

Deria, P., Gómez-Gualdrón, D. A., Bury, W., Schaef, H. T., Wang, T. C., Thallapally, P. K., ... Farha, O. K. (2015). Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology. Journal of the American Chemical Society, 137(40), 13183-13190. https://doi.org/10.1021/jacs.5b08860

Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology. / Deria, Pravas; Gómez-Gualdrón, Diego A.; Bury, Wojciech; Schaef, Herbert T.; Wang, Timothy C.; Thallapally, Praveen K.; Sarjeant, Amy A.; Snurr, Randall Q.; Hupp, Joseph T; Farha, Omar K.

In: Journal of the American Chemical Society, Vol. 137, No. 40, 14.10.2015, p. 13183-13190.

Research output: Contribution to journalArticle

Deria, P, Gómez-Gualdrón, DA, Bury, W, Schaef, HT, Wang, TC, Thallapally, PK, Sarjeant, AA, Snurr, RQ, Hupp, JT & Farha, OK 2015, 'Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology', Journal of the American Chemical Society, vol. 137, no. 40, pp. 13183-13190. https://doi.org/10.1021/jacs.5b08860
Deria P, Gómez-Gualdrón DA, Bury W, Schaef HT, Wang TC, Thallapally PK et al. Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology. Journal of the American Chemical Society. 2015 Oct 14;137(40):13183-13190. https://doi.org/10.1021/jacs.5b08860
Deria, Pravas ; Gómez-Gualdrón, Diego A. ; Bury, Wojciech ; Schaef, Herbert T. ; Wang, Timothy C. ; Thallapally, Praveen K. ; Sarjeant, Amy A. ; Snurr, Randall Q. ; Hupp, Joseph T ; Farha, Omar K. / Ultraporous, water stable, and breathing zirconium-based metal-organic frameworks with ftw topology. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 40. pp. 13183-13190.
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AU - Gómez-Gualdrón, Diego A.

AU - Bury, Wojciech

AU - Schaef, Herbert T.

AU - Wang, Timothy C.

AU - Thallapally, Praveen K.

AU - Sarjeant, Amy A.

AU - Snurr, Randall Q.

AU - Hupp, Joseph T

AU - Farha, Omar K.

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