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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

141 Scopus citations


"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 (US)
Pages (from-to)13183-13190
Number of pages8
JournalJournal of the American Chemical Society
Issue number40
StatePublished - Oct 14 2015

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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