4.8 Article

Rapid desolvation-triggered domino lattice rearrangement in a metal-organic framework

Journal

NATURE CHEMISTRY
Volume 12, Issue 1, Pages 90-97

Publisher

NATURE RESEARCH
DOI: 10.1038/s41557-019-0364-0

Keywords

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Funding

  1. Ministry of Science and Technology, Taiwan [MOST-106-2113-M-033-001, MOST-106-2113-M-007-023-MY2, MOST-1032113-M-001-005-MY3]
  2. Chung Yuan Christian University
  3. Robert A. Welch Foundation through a Welch Endowed Chair [A-0030]
  4. National Tsing Hua University
  5. Academia Sinica
  6. US Department of Energy [DE-FG02-08ER46491, DE-SC0019902]
  7. National Synchrotron Radiation Research Center (NSRRC), Taiwan
  8. US Department of Energy, Office of Science (DOE-BES) [DE-SC0017864]
  9. US Department of Energy, Office of Basic Energy Sciences (DOE-BES) [DE-SC0017864]
  10. Knut and Alice Wallenberg Foundation (KAW) (3DEM-NATUR project) [2012.0112]
  11. Swedish Research Council (VR) [2017-04321]
  12. NSF MRSEC programme through Columbia University in the Center for Precision Assembly of Superstratic and Superatomic Solids [DMR-1420634]
  13. US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0012704]
  14. U.S. Department of Energy (DOE) [DE-SC0019902, DE-FG02-08ER46491] Funding Source: U.S. Department of Energy (DOE)

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Topological transitions between considerably different phases typically require harsh conditions to collectively break chemical bonds and overcome the stress caused to the original structure by altering its correlated bond environment. In this work we present a case system that can achieve rapid rearrangement of the whole lattice of a metal-organic framework through a domino alteration of the bond connectivity under mild conditions. The system transforms from a disordered metal-organic framework with low porosity to a highly porous and crystalline isomer within 40s following activation (solvent exchange and desolvation), resulting in a substantial increase in surface area from 725 to 2,749 m(2) g(-1). Spectroscopic measurements show that this counter-intuitive lattice rearrangement involves a metastable intermediate that results from solvent removal on coordinatively unsaturated metal sites. This disordered-crystalline switch between two topological distinct metal-organic frameworks is shown to be reversible over four cycles through activation and reimmersion in polar solvents.

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