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Title: An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra

Abstract

We report the rational design and synthesis of a water-stable metal–organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe3+-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based construction, Fe-HAF-1 displays exceptional chemical stability in organic and aqueous solvents over a wide pH range (pH 1–14), including in the presence of 5 M NaOH. Despite the charge neutrality of the Fe3+-tris(hydroxamate) centers, Fe-HAF-1 crystals are negatively charged above pH 4. This unexpected property is attributed to the formation of defects during crystallization that results in uncoordinated hydroxamate ligands or hydroxide-coordinated Fe centers. The anionic nature of Fe-HAF-1 crystals enables selective adsorption of positively charged ions in aqueous solution, resulting in efficient separation of organic dyes and other charged species in a size-selective fashion. Fe-HAF-1 presents a new addition to a small group of chelate-based MOFs and provides a rare framework whose 3D connectivity is exclusively formed by metal–hydroxamate coordination.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, San Diego, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); University of California, San Diego, La Jolla, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Institutes of Health (NIH); National Science Foundation (NSF)
OSTI Identifier:
1656873
Alternate Identifier(s):
OSTI ID: 1668315
Grant/Contract Number:  
AC02-06CH11357; SC0003844; T32GM112584; CHE-1661655; CHE-1338173
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 15; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 36 MATERIALS SCIENCE; Design; reticular chemistry; dyes and pigments; metals; ligands; metal organic frameworks; cluster chemistry

Citation Formats

Chiong, Jerika A., Zhu, Jie, Bailey, Jake B., Kalaj, Mark, Subramanian, Rohit H., Xu, Wenqian, Cohen, Seth M., and Tezcan, F. Akif. An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra. United States: N. p., 2020. Web. doi:10.1021/jacs.0c01626.
Chiong, Jerika A., Zhu, Jie, Bailey, Jake B., Kalaj, Mark, Subramanian, Rohit H., Xu, Wenqian, Cohen, Seth M., & Tezcan, F. Akif. An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra. United States. https://doi.org/10.1021/jacs.0c01626
Chiong, Jerika A., Zhu, Jie, Bailey, Jake B., Kalaj, Mark, Subramanian, Rohit H., Xu, Wenqian, Cohen, Seth M., and Tezcan, F. Akif. Sat . "An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra". United States. https://doi.org/10.1021/jacs.0c01626. https://www.osti.gov/servlets/purl/1656873.
@article{osti_1656873,
title = {An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra},
author = {Chiong, Jerika A. and Zhu, Jie and Bailey, Jake B. and Kalaj, Mark and Subramanian, Rohit H. and Xu, Wenqian and Cohen, Seth M. and Tezcan, F. Akif},
abstractNote = {We report the rational design and synthesis of a water-stable metal–organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe3+-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based construction, Fe-HAF-1 displays exceptional chemical stability in organic and aqueous solvents over a wide pH range (pH 1–14), including in the presence of 5 M NaOH. Despite the charge neutrality of the Fe3+-tris(hydroxamate) centers, Fe-HAF-1 crystals are negatively charged above pH 4. This unexpected property is attributed to the formation of defects during crystallization that results in uncoordinated hydroxamate ligands or hydroxide-coordinated Fe centers. The anionic nature of Fe-HAF-1 crystals enables selective adsorption of positively charged ions in aqueous solution, resulting in efficient separation of organic dyes and other charged species in a size-selective fashion. Fe-HAF-1 presents a new addition to a small group of chelate-based MOFs and provides a rare framework whose 3D connectivity is exclusively formed by metal–hydroxamate coordination.},
doi = {10.1021/jacs.0c01626},
journal = {Journal of the American Chemical Society},
number = 15,
volume = 142,
place = {United States},
year = {Sat Mar 28 00:00:00 EDT 2020},
month = {Sat Mar 28 00:00:00 EDT 2020}
}

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Works referenced in this record:

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Honeycomb Metal–Organic Framework with Lewis Acidic and Basic Bifunctional Sites: Selective Adsorption and CO 2 Catalytic Fixation
journal, March 2018

  • Li, Xiu-Yuan; Ma, Li-Na; Liu, Yang
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 13
  • DOI: 10.1021/acsami.8b01291

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis
journal, January 2014

  • Liu, Jiewei; Chen, Lianfen; Cui, Hao
  • Chemical Society Reviews, Vol. 43, Issue 16, p. 6011-6061
  • DOI: 10.1039/C4CS00094C

Metal–Organic Frameworks in Solid–Gas Phase Catalysis
journal, November 2018


Highly Stable Zr(IV)-Based Metal–Organic Frameworks with Chiral Phosphoric Acids for Catalytic Asymmetric Tandem Reactions
journal, April 2019

  • Gong, Wei; Chen, Xu; Jiang, Hong
  • Journal of the American Chemical Society, Vol. 141, Issue 18
  • DOI: 10.1021/jacs.9b02294

Metal-Organic Frameworks for CO 2 Chemical Transformations
journal, October 2016


A New Class of Metal-Cyclam-Based Zirconium Metal–Organic Frameworks for CO 2 Adsorption and Chemical Fixation
journal, January 2018

  • Zhu, Jie; Usov, Pavel M.; Xu, Wenqian
  • Journal of the American Chemical Society, Vol. 140, Issue 3
  • DOI: 10.1021/jacs.7b10643

The role of reticular chemistry in the design of CO2 reduction catalysts
journal, February 2018


Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

Metal-Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy
journal, March 2017


Temperature Treatment of Highly Porous Zirconium-Containing Metal–Organic Frameworks Extends Drug Delivery Release
journal, May 2017

  • Teplensky, Michelle H.; Fantham, Marcus; Li, Peng
  • Journal of the American Chemical Society, Vol. 139, Issue 22
  • DOI: 10.1021/jacs.7b01451

Metal–organic framework membranes: from synthesis to separation application
journal, January 2014

  • Qiu, Shilun; Xue, Ming; Zhu, Guangshan
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00159A

Microporous Metal-Organic Framework Materials for Gas Separation
journal, February 2020


Controlling guest conformation for efficient purification of butadiene
journal, June 2017


Design and control of gas diffusion process in a nanoporous soft crystal
journal, January 2019


Photochemistry and photophysics of MOFs: steps towards MOF-based sensing enhancements
journal, January 2018

  • Dolgopolova, Ekaterina A.; Rice, Allison M.; Martin, Corey R.
  • Chemical Society Reviews, Vol. 47, Issue 13
  • DOI: 10.1039/C7CS00861A

Topological Analysis of Metal–Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle
journal, November 2013

  • Li, Mian; Li, Dan; O’Keeffe, Michael
  • Chemical Reviews, Vol. 114, Issue 2
  • DOI: 10.1021/cr400392k

Secondary building units as the turning point in the development of the reticular chemistry of MOFs
journal, October 2018

  • Kalmutzki, Markus J.; Hanikel, Nikita; Yaghi, Omar M.
  • Science Advances, Vol. 4, Issue 10
  • DOI: 10.1126/sciadv.aat9180

Establishing Microporosity in Open Metal−Organic Frameworks:  Gas Sorption Isotherms for Zn(BDC) (BDC = 1,4-Benzenedicarboxylate)
journal, August 1998

  • Li, Hailian; Eddaoudi, Mohamed; Groy, Thomas L.
  • Journal of the American Chemical Society, Vol. 120, Issue 33, p. 8571-8572
  • DOI: 10.1021/ja981669x

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications
journal, February 2018


Siderophore-inspired chelator hijacks uranium from aqueous medium
journal, February 2019

  • Ivanov, Alexander S.; Parker, Bernard F.; Zhang, Zhicheng
  • Nature Communications, Vol. 10, Issue 1
  • DOI: 10.1038/s41467-019-08758-1

Siderophores: Structure and Function of Microbial Iron Transport Compounds
journal, November 1995


Iron bioavailability and the coordination chemistry of hydroxamic acids
journal, November 1990


Towards hydroxamic acid linked zirconium metal–organic frameworks
journal, January 2017

  • Pereira, Carla F.; Howarth, Ashlee J.; Vermeulen, Nicolaas A.
  • Materials Chemistry Frontiers, Vol. 1, Issue 6
  • DOI: 10.1039/C6QM00364H

Hydroxamate Titanium–Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity
journal, July 2019

  • Padial, Natalia M.; Castells-Gil, Javier; Almora-Barrios, Neyvis
  • Journal of the American Chemical Society, Vol. 141, Issue 33
  • DOI: 10.1021/jacs.9b04915

Coordination Polymers of 2,5-Dihydroxybenzoquinone and Chloranilic Acid with the (10,3)- a Topology
journal, July 2011

  • Abrahams, Brendan F.; Hudson, Timothy A.; McCormick, Laura J.
  • Crystal Growth & Design, Vol. 11, Issue 7
  • DOI: 10.1021/cg2005908

Monometallic Lanthanoid Assembly Showing Ferromagnetism with a Curie Temperature of 11 K
journal, September 2009

  • Nakabayashi, Koji; Ohkoshi, Shin-ichi
  • Inorganic Chemistry, Vol. 48, Issue 18
  • DOI: 10.1021/ic900625a

New Porous Crystals of Extended Metal-Catecholates
journal, August 2012

  • Hmadeh, Mohamad; Lu, Zheng; Liu, Zheng
  • Chemistry of Materials, Vol. 24, Issue 18, p. 3511-3513
  • DOI: 10.1021/cm301194a

Three-Dimensional Metal-Catecholate Frameworks and Their Ultrahigh Proton Conductivity
journal, December 2015

  • Nguyen, Nhung T. T.; Furukawa, Hiroyasu; Gándara, Felipe
  • Journal of the American Chemical Society, Vol. 137, Issue 49
  • DOI: 10.1021/jacs.5b10999

A Metal Organic Framework with Spherical Protein Nodes: Rational Chemical Design of 3D Protein Crystals
journal, September 2015

  • Sontz, Pamela A.; Bailey, Jake B.; Ahn, Sunhyung
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b07463

Synthetic Modularity of Protein–Metal–Organic Frameworks
journal, June 2017

  • Bailey, Jake B.; Zhang, Ling; Chiong, Jerika A.
  • Journal of the American Chemical Society, Vol. 139, Issue 24
  • DOI: 10.1021/jacs.7b01202

Large M 4 L 4 (M = Al(III), Ga(III), In(III), Ti(IV)) Tetrahedral Coordination Cages:  an Extension of Symmetry-Based Design
journal, September 2005

  • Yeh, Robert M.; Xu, Jide; Seeber, Georg
  • Inorganic Chemistry, Vol. 44, Issue 18
  • DOI: 10.1021/ic0505145

Cages with Tetrahedron-Like Topology Formed from the Combination of Cyclotricatechylene Ligands with Metal Cations
journal, March 2010

  • Abrahams, Brendan F.; FitzGerald, Nicholas J.; Robson, Richard
  • Angewandte Chemie International Edition, Vol. 49, Issue 16
  • DOI: 10.1002/anie.201000149

Symmetry-Based Metal Complex Cluster Formation
journal, June 1996

  • Beissel, Thomas; Powers, Ryan E.; Raymond, Kenneth N.
  • Angewandte Chemie International Edition in English, Vol. 35, Issue 10
  • DOI: 10.1002/anie.199610841

Metal–organic macrocycles, metal–organic polyhedra and metal–organic frameworks
journal, January 2009

  • Prakash, M. Jaya; Lah, Myoung Soo
  • Chemical Communications, Issue 23
  • DOI: 10.1039/b902988e

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

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

A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction
journal, August 2004

  • Férey, Gérard; Serre, Christian; Mellot-Draznieks, Caroline
  • Angewandte Chemie International Edition, Vol. 43, Issue 46
  • DOI: 10.1002/anie.200460592

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
journal, June 2006

  • Park, K. S.; Ni, Z.; Cote, A. P.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191
  • DOI: 10.1073/pnas.0602439103

Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit
journal, January 2013

  • DeCoste, Jared B.; Peterson, Gregory W.; Jasuja, Himanshu
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10662d

Improving MOF stability: approaches and applications
journal, January 2019

  • Ding, Meili; Cai, Xuechao; Jiang, Hai-Long
  • Chemical Science, Vol. 10, Issue 44
  • DOI: 10.1039/C9SC03916C

Defective Metal-Organic Frameworks
journal, January 2018

  • Dissegna, Stefano; Epp, Konstantin; Heinz, Werner R.
  • Advanced Materials, Vol. 30, Issue 37
  • DOI: 10.1002/adma.201704501

Effects of the preassembly of benzohydroxamic acid with Fe (III) ions on its adsorption on cassiterite surface
journal, October 2018


Polyhydroxamic acid functionalized sorbent for effective removal of chromium from ground water and chromic acid cleaning bath
journal, October 2017


Reductometric Titration and Quantum Chemical Study of Oxalohydroxamic Acid for Determination of Manganese in Ores and Alloys
journal, January 2017

  • Agrawal, Sonalika; Khan, Fahmida; Verma, Dakeshwar Kumar
  • Asian Journal of Chemistry, Vol. 29, Issue 12
  • DOI: 10.14233/ajchem.2017.20719

Efficient degradation of high concentration azo-dye wastewater by heterogeneous Fenton process with iron-based metal-organic framework
journal, May 2015


Ionic metal-organic frameworks (iMOFs): Design principles and applications
journal, January 2016

  • Karmakar, Avishek; Desai, Aamod V.; Ghosh, Sujit K.
  • Coordination Chemistry Reviews, Vol. 307
  • DOI: 10.1016/j.ccr.2015.08.007

Selective anion exchange with nanogated isoreticular positive metal-organic frameworks
journal, August 2013

  • Zhao, Xiang; Bu, Xianhui; Wu, Tao
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3344

Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic Framework (MOF) with Ultra Large Pores
journal, July 2016

  • Li, Peng; Vermeulen, Nicolaas A.; Gong, Xirui
  • Angewandte Chemie International Edition, Vol. 55, Issue 35
  • DOI: 10.1002/anie.201605547

A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants
journal, November 2017


The role of the counter-ion in metal-organic frameworks’ chemistry and applications
journal, December 2018


Tuning the Ionicity of Stable Metal–Organic Frameworks through Ionic Linker Installation
journal, January 2019

  • Pang, Jiandong; Yuan, Shuai; Qin, Jun-Sheng
  • Journal of the American Chemical Society, Vol. 141, Issue 7
  • DOI: 10.1021/jacs.8b12530

Four MOFs with 2,2′-dimethoxy-4,4′-biphenyldicarboxylic acid: syntheses, structures, topologies and properties
journal, January 2014


Stable dye-encapsulated indium–organic framework as dual-emitting sensor for the detection of Hg 2+ /Cr 2 O 7 2− and a wide range of nitro-compounds
journal, January 2018

  • Fu, Hong-Ru; Zhao, Ying; Xie, Tao
  • Journal of Materials Chemistry C, Vol. 6, Issue 24
  • DOI: 10.1039/C8TC01571F

Dual-emission MOF⊃dye sensor for ratiometric fluorescence recognition of RDX and detection of a broad class of nitro-compounds
journal, January 2018

  • Fu, Hong-Ru; Yan, Li-Bing; Wu, Nai-Teng
  • Journal of Materials Chemistry A, Vol. 6, Issue 19
  • DOI: 10.1039/C8TA02857E

Design, Formation and Properties of Tetrahedral M 4 L 4 and M 4 L 6 Supramolecular Clusters 1
journal, September 2001

  • Caulder, Dana L.; Brückner, Christian; Powers, Ryan E.
  • Journal of the American Chemical Society, Vol. 123, Issue 37
  • DOI: 10.1021/ja0104507

Self-Assembly of Discrete Cyclic Nanostructures Mediated by Transition Metals
journal, March 2000

  • Leininger, Stefan; Olenyuk, Bogdan; Stang, Peter J.
  • Chemical Reviews, Vol. 100, Issue 3
  • DOI: 10.1021/cr9601324

Strategies for the Construction of Supramolecular Compounds through Coordination Chemistry
journal, June 2001


Functional Molecular Flasks: New Properties and Reactions within Discrete, Self-Assembled Hosts
journal, April 2009

  • Yoshizawa, Michito; Klosterman, Jeremy K.; Fujita, Makoto
  • Angewandte Chemie International Edition, Vol. 48, Issue 19, p. 3418-3438
  • DOI: 10.1002/anie.200805340