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

Abstract

Topological transitions between significantly different phases typically require extreme 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 (MOF) through a ‘domino’ alteration of the bond connectivity under mild conditions. The system transforms from a disordered amorphous MOF with low porosity to a highly porous and crystalline isomer within 40 seconds upon activation (solvent exchange and desorption), resulting in a significant increase in surface area, from 725 to 2,749 m2/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. In conclusion, this amorphous–crystalline switch between two topological distinct MOFs is shown to be reversible over four cycles through activation and re-immersion in polar solvents.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [2];  [2];  [5];  [6];  [2];  [7];  [6];  [8]; ORCiD logo [9]; ORCiD logo [10]; ORCiD logo [11]; ORCiD logo [8];  [8];  [4]; ORCiD logo [2]
  1. National Tsing Hua University, Hsinchu (Taiwan); Academia Sinica, Taipei Taiwan)
  2. Texas A & M Univ., College Station, TX (United States)
  3. Univ. of Texas at Dallas, Richardson, TX (United States)
  4. Stockholm Univ. (Sweden)
  5. National Tsing Hua University, Hsinchu (Taiwan)
  6. Chung Yuan Christian University, Taoyuan City (Taiwan)
  7. Columbia Univ., New York, NY (United States)
  8. Academia Sinica, Taipei (Taiwan)
  9. Chung Yuan Christian University, Taoyuan City (Taiwan); National Taiwan Normal University, Taipei (Taiwan)
  10. National Tsing Hua University, Hsinchu (Taiwan); Chung Yuan Christian University, Taoyuan City (Taiwan)
  11. Columbia Univ., New York, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Univ. of Texas at Dallas, Richardson, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1643793
Grant/Contract Number:  
SC0019902; FG02-08ER46491; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Coordination chemistry; Metal–organic frameworks

Citation Formats

Lo, Sheng-Han, Feng, Liang, Tan, Kui, Huang, Zhehao, Yuan, Shuai, Wang, Kun-Yu, Li, Bing-Han, Liu, Wan-Ling, Day, Gregory S., Tao, Songsheng, Yang, Chun-Chuen, Luo, Tzuoo-Tsair, Lin, Chia-Her, Wang, Sue-Lein, Billinge, Simon J. L., Lu, Kuang-Lieh, Chabal, Yves J., Zou, Xiaodong, and Zhou, Hong-Cai. Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework. United States: N. p., 2019. Web. https://doi.org/10.1038/s41557-019-0364-0.
Lo, Sheng-Han, Feng, Liang, Tan, Kui, Huang, Zhehao, Yuan, Shuai, Wang, Kun-Yu, Li, Bing-Han, Liu, Wan-Ling, Day, Gregory S., Tao, Songsheng, Yang, Chun-Chuen, Luo, Tzuoo-Tsair, Lin, Chia-Her, Wang, Sue-Lein, Billinge, Simon J. L., Lu, Kuang-Lieh, Chabal, Yves J., Zou, Xiaodong, & Zhou, Hong-Cai. Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework. United States. https://doi.org/10.1038/s41557-019-0364-0
Lo, Sheng-Han, Feng, Liang, Tan, Kui, Huang, Zhehao, Yuan, Shuai, Wang, Kun-Yu, Li, Bing-Han, Liu, Wan-Ling, Day, Gregory S., Tao, Songsheng, Yang, Chun-Chuen, Luo, Tzuoo-Tsair, Lin, Chia-Her, Wang, Sue-Lein, Billinge, Simon J. L., Lu, Kuang-Lieh, Chabal, Yves J., Zou, Xiaodong, and Zhou, Hong-Cai. Mon . "Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework". United States. https://doi.org/10.1038/s41557-019-0364-0. https://www.osti.gov/servlets/purl/1643793.
@article{osti_1643793,
title = {Rapid desolvation-triggered domino lattice rearrangement in a metal–organic framework},
author = {Lo, Sheng-Han and Feng, Liang and Tan, Kui and Huang, Zhehao and Yuan, Shuai and Wang, Kun-Yu and Li, Bing-Han and Liu, Wan-Ling and Day, Gregory S. and Tao, Songsheng and Yang, Chun-Chuen and Luo, Tzuoo-Tsair and Lin, Chia-Her and Wang, Sue-Lein and Billinge, Simon J. L. and Lu, Kuang-Lieh and Chabal, Yves J. and Zou, Xiaodong and Zhou, Hong-Cai},
abstractNote = {Topological transitions between significantly different phases typically require extreme 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 (MOF) through a ‘domino’ alteration of the bond connectivity under mild conditions. The system transforms from a disordered amorphous MOF with low porosity to a highly porous and crystalline isomer within 40 seconds upon activation (solvent exchange and desorption), resulting in a significant increase in surface area, from 725 to 2,749 m2/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. In conclusion, this amorphous–crystalline switch between two topological distinct MOFs is shown to be reversible over four cycles through activation and re-immersion in polar solvents.},
doi = {10.1038/s41557-019-0364-0},
journal = {Nature Chemistry},
number = 1,
volume = 12,
place = {United States},
year = {2019},
month = {12}
}

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Works referenced in this record:

Rapid Guest Exchange and Ultra-Low Surface Tension Solvents Optimize Metal-Organic Framework Activation
journal, October 2017

  • Ma, Jialiu; Kalenak, Andre P.; Wong-Foy, Antek G.
  • Angewandte Chemie International Edition, Vol. 56, Issue 46
  • DOI: 10.1002/anie.201709187

Hierarchical nanofabrication of microporous crystals with ordered mesoporosity
journal, October 2008

  • Fan, Wei; Snyder, Mark A.; Kumar, Sandeep
  • Nature Materials, Vol. 7, Issue 12
  • DOI: 10.1038/nmat2302

Opening the Gate: Framework Flexibility in ZIF-8 Explored by Experiments and Simulations
journal, June 2011

  • Fairen-Jimenez, D.; Moggach, S. A.; Wharmby, M. T.
  • Journal of the American Chemical Society, Vol. 133, Issue 23
  • DOI: 10.1021/ja202154j

Structural Effects of Solvents on the Breathing of Metal–Organic Frameworks: An In Situ Diffraction Study
journal, May 2008

  • Millange, Franck; Serre, Christian; Guillou, Nathalie
  • Angewandte Chemie International Edition, Vol. 47, Issue 22
  • DOI: 10.1002/anie.200705607

A supermolecular building approach for the design and construction of metal–organic frameworks
journal, January 2014

  • Guillerm, Vincent; Kim, Dongwook; Eubank, Jarrod F.
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00135D

Flexible metal–organic frameworks
journal, January 2014

  • Schneemann, A.; Bon, V.; Schwedler, I.
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00101J

Defibrillation of soft porous metal-organic frameworks with electric fields
journal, October 2017


Coordination change, lability and hemilability in metal–organic frameworks
journal, January 2017

  • Morris, Russell E.; Brammer, Lee
  • Chemical Society Reviews, Vol. 46, Issue 17
  • DOI: 10.1039/C7CS00187H

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework
journal, June 2009

  • Xiao, Bo; Byrne, Peter J.; Wheatley, Paul S.
  • Nature Chemistry, Vol. 1, Issue 4
  • DOI: 10.1038/nchem.254

Effect of Dehydration on the Local Structure of Framework Aluminum Atoms in Mixed Linker MIL-53(Al) Materials Studied by Solid-State NMR Spectroscopy
journal, September 2010

  • Jiang, Yijiao; Huang, Jun; Marx, Stefan
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 19
  • DOI: 10.1021/jz1010835

Rational Design, Synthesis, Purification, and Activation of Metal−Organic Framework Materials
journal, August 2010

  • Farha, Omar K.; Hupp, Joseph T.
  • Accounts of Chemical Research, Vol. 43, Issue 8, p. 1166-1175
  • DOI: 10.1021/ar1000617

In Situ Single-Crystal Diffraction Studies of the Structural Transition of Metal−Organic Framework Copper 5-Sulfoisophthalate, Cu-SIP-3
journal, March 2010

  • Allan, Phoebe K.; Xiao, Bo; Teat, Simon J.
  • Journal of the American Chemical Society, Vol. 132, Issue 10
  • DOI: 10.1021/ja910600b

Protein folding and misfolding
journal, December 2003


Probing the adsorption performance of the hybrid porous MIL-68(Al): a synergic combination of experimental and modelling tools
journal, January 2012

  • Yang, Qingyuan; Vaesen, Sébastien; Vishnuvarthan, Muthusamy
  • Journal of Materials Chemistry, Vol. 22, Issue 20
  • DOI: 10.1039/c2jm15609a

A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration
journal, March 2004

  • Loiseau, Thierry; Serre, Christian; Huguenard, Clarisse
  • Chemistry - A European Journal, Vol. 10, Issue 6
  • DOI: 10.1002/chem.200305413

Correlated defect nanoregions in a metal–organic framework
journal, June 2014

  • Cliffe, Matthew J.; Wan, Wei; Zou, Xiaodong
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5176

Solvent-switchable continuous-breathing behaviour in a diamondoid metal–organic framework and its influence on CO2 versus CH4 selectivity
journal, March 2017

  • Carrington, Elliot J.; McAnally, Craig A.; Fletcher, Ashleigh J.
  • Nature Chemistry, Vol. 9, Issue 9
  • DOI: 10.1038/nchem.2747

Role of Solvent-Host Interactions That Lead to Very Large Swelling of Hybrid Frameworks
journal, March 2007


Metal-organic frameworks based on iron oxide octahedral chains connected by benzenedicarboxylate dianions
journal, September 2005


Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute
journal, June 2014

  • Kao, Joseph; Thorkelsson, Kari; Bai, Peter
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5053

Liquid metal–organic frameworks
journal, October 2017

  • Gaillac, Romain; Pullumbi, Pluton; Beyer, Kevin A.
  • Nature Materials, Vol. 16, Issue 11
  • DOI: 10.1038/nmat4998

Hybrid glasses from strong and fragile metal-organic framework liquids
journal, August 2015

  • Bennett, Thomas D.; Tan, Jin-Chong; Yue, Yuanzheng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9079

Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts
journal, June 2016

  • Yuan, Shuai; Zou, Lanfang; Li, Haixia
  • Angewandte Chemie International Edition, Vol. 55, Issue 36
  • DOI: 10.1002/anie.201604313

Adsorption and molecular siting of CO 2 , water, and other gases in the superhydrophobic, flexible pores of FMOF-1 from experiment and simulation
journal, January 2017

  • Moghadam, Peyman Z.; Ivy, Joshua F.; Arvapally, Ravi K.
  • Chemical Science, Vol. 8, Issue 5
  • DOI: 10.1039/C7SC00278E

Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks
journal, September 2016


Redox-switchable breathing behavior in tetrathiafulvalene-based metal–organic frameworks
journal, December 2017


Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids MIL-53 or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}x·H2Oy
journal, November 2002

  • Serre, Christian; Millange, Franck; Thouvenot, Christelle
  • Journal of the American Chemical Society, Vol. 124, Issue 45, p. 13519-13526
  • DOI: 10.1021/ja0276974

Methane storage in flexible metal–organic frameworks with intrinsic thermal management
journal, October 2015

  • Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K.
  • Nature, Vol. 527, Issue 7578
  • DOI: 10.1038/nature15732

Reversible Interpenetration in a Metal-Organic Framework Triggered by Ligand Removal and Addition
journal, July 2012

  • Choi, Sang Beom; Furukawa, Hiroyasu; Nam, Hye Jin
  • Angewandte Chemie International Edition, Vol. 51, Issue 35, p. 8791-8795
  • DOI: 10.1002/anie.201202925

Self-assembly of polyhedral metal–organic framework particles into three-dimensional ordered superstructures
journal, October 2017

  • Avci, Civan; Imaz, Inhar; Carné-Sánchez, Arnau
  • Nature Chemistry, Vol. 10, Issue 1
  • DOI: 10.1038/nchem.2875

Structural disorder in molecular framework materials
journal, January 2013

  • Cairns, Andrew B.; Goodwin, Andrew L.
  • Chemical Society Reviews, Vol. 42, Issue 12
  • DOI: 10.1039/c3cs35524a

Predicting the energetics of osmolyte-induced protein folding/unfolding
journal, October 2005

  • Auton, M.; Bolen, D. W.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 42
  • DOI: 10.1073/pnas.0507053102

Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer
journal, October 2007

  • Ghosh, Sujit K.; Zhang, Jie-Peng; Kitagawa, Susumu
  • Angewandte Chemie International Edition, Vol. 46, Issue 42
  • DOI: 10.1002/anie.200703086

Zipping and Unzipping of a Paddlewheel Metal-Organic Framework to Enable Two-Step Synthetic and Structural Transformation
journal, February 2013

  • Smart, Paul; Mason, Charles A.; Loader, Jason R.
  • Chemistry - A European Journal, Vol. 19, Issue 11
  • DOI: 10.1002/chem.201204492

Reversible Solid-to-Liquid Phase Transition of Coordination Polymer Crystals
journal, January 2015

  • Umeyama, Daiki; Horike, Satoshi; Inukai, Munehiro
  • Journal of the American Chemical Society, Vol. 137, Issue 2
  • DOI: 10.1021/ja511019u

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Protein Folding and Unfolding at Atomic Resolution
journal, February 2002


The Structure of the Aluminum Fumarate Metal-Organic Framework A520
journal, February 2015

  • Alvarez, Elsa; Guillou, Nathalie; Martineau, Charlotte
  • Angewandte Chemie International Edition, Vol. 54, Issue 12
  • DOI: 10.1002/anie.201410459

Reversible Topochemical Transformation of a Soft Crystal of a Coordination Polymer
journal, October 2007

  • Ghosh, Sujit K.; Zhang, Jie-Peng; Kitagawa, Susumu
  • Angewandte Chemie, Vol. 119, Issue 42
  • DOI: 10.1002/ange.200703086

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie, Vol. 127, Issue 49
  • DOI: 10.1002/ange.201505625

Rapid Guest Exchange and Ultra-Low Surface Tension Solvents Optimize Metal-Organic Framework Activation
journal, October 2017

  • Ma, Jialiu; Kalenak, Andre P.; Wong-Foy, Antek G.
  • Angewandte Chemie, Vol. 129, Issue 46
  • DOI: 10.1002/ange.201709187