A subscription to JoVE is required to view this content. Sign in or start your free trial.

In This Article

  • Summary
  • Abstract
  • Introduction
  • Protocol
  • Results
  • Discussion
  • Disclosures
  • Acknowledgements
  • Materials
  • References
  • Reprints and Permissions

Summary

Post-synthetic ligand exchange (PSE) is a versatile and powerful tool for installing functional groups into metal-organic frameworks (MOFs). Exposing MOFs to solutions containing triazole- and tetrazole-functionalized ligands can incorporate these heterocyclic moieties into Zr-MOFs through PSE processes.

Abstract

Metal-organic frameworks (MOFs) are a class of porous materials that are formed through coordination bonds between metal clusters and organic ligands. Given their coordinative nature, the organic ligands and strut framework can be readily removed from the MOF and/or exchanged with other coordinative molecules. By introducing target ligands to MOF-containing solutions, functionalized MOFs can be obtained with new chemical tags via a process called post-synthetic ligand exchange (PSE). PSE is a straightforward and practical approach that enables the preparation of a wide range of MOFs with new chemical tags via a solid-solution equilibrium process. Furthermore, PSE can be performed at room temperature, allowing the incorporation of thermally unstable ligands into MOFs. In this work, we demonstrate the practicality of PSE by using heterocyclic triazole- and tetrazole-containing ligands to functionalize a Zr-based MOF (UiO-66; UiO = University of Oslo). After digestion, the functionalized MOFs are characterized via various techniques, including powder X-ray diffraction and nuclear magnetic resonance spectroscopy.

Introduction

Metal-organic frameworks (MOFs) are three-dimensional porous materials that are formed through coordination bonds between metal clusters and multi-topic organic ligands. MOFs have garnered significant attention due to their permanent porosity, low density, and ability to associate organic and inorganic components, which enables diverse applications1,2. Moreover, the vast range of metal nodes and strut organic linkers offer MOFs theoretically unlimited structural combinations. Even with identical framework structures, MOFs' physical and chemical properties can be modified through ligand functionalization with chemical tags. This modification process offers a promising route to tailor the properties of MOFs for specific applications3,4,5,6,7,8,9.

Both the pre-functionalization of ligands prior to MOF synthesis and post-synthetic modification (PSM) of MOFs have been employed to introduce and/or modify functional groups in MOF ligands10,11. In particular, covalent PSMs have been extensively studied to introduce new functional groups and generate a range of MOFs with diverse functionalities12,13,14. For instance, UiO-66-NH2 can be converted to amide-functionalized UiO-66-AMs with different chain lengths (ranging from the shortest acetamide to the longest n-hexyl amide) through acylation reactions with appropriate acyl halides (such as acetyl chloride or n-hexanoyl chloride)15,16. This approach demonstrates the versatility of covalent PSMs to introduce specific functional groups onto MOF ligands, paving the way for a broad range of applications.

In addition to covalent PSMs, post-synthetic ligand exchange (PSE) is a promising strategy for modifying MOFs (Figure 1). Since MOFs are composed of coordination bonds between metals and ligands (such as carboxylates), these coordination bonds can be replaced with external ligands from a solution. Exposing MOFs to a solution containing the desired ligand with chemical tags can be incorporated into the MOFs via PSE17,18,19,20,21,22. Since the PSE process is accelerated by the existence of coordinative solvents, the phenomenon is also called solvent-assisted ligand exchange (SALE)23,24. This approach offers a flexible and facile method for functionalizing MOFs with a wide range of external ligands, enabling a broad spectrum of applications25,26,27,28,29.

figure-introduction-3480
Figure 1: Synthesis of triazole and tetrazole-functionalized H2BDC ligands and preparation of triazole- and tetrazole-functionalized UiO-66 MOF through PSE. Please click here to view a larger version of this figure.

The progress of the PSE process can be controlled by adjusting the ligand ratio, exchange temperature, and time. Notably, room temperature PSE can be employed to obtain functionalized MOFs by exchanging ligands from a solution into MOF solids20. The PSE strategy is particularly useful for introducing both thermally unstable functional groups (such as azido groups) and coordinative functional groups (such as phenol groups) into MOF structures18. In addition, the PSE strategy has been applied to various MOFs with metal and coordination bond variations. This exchange is a universal process in the chemistry of MOFs30,31,32. In this study, we present a detailed protocol for PSE to obtain functionalized MOFs from pristine, non-functionalized MOFs, and we provide a characterization strategy to confirm successful functionalization of the MOFs. This method demonstrates the versatility and convenience of PSE for modifying MOFs with diverse functional groups.

Tetrazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Tetrazole)33, and triazole-containing benzene-1,4-dicarboxylic acid (H2BDC-Triazole) are synthesized as target ligands and utilized in the PSE of UiO-66 MOFs to obtain novel, coordination-free, triazole-containing MOFs. Both triazoles and tetrazoles possess acidic N-H protons on their heterocyclic rings and can coordinate with metal cations, thus enabling their use in constructing MOFs34,35. However, there are limited studies on incorporating coordination-free tetrazoles and triazoles into MOFs and related structures. In case of triazole-functionalized Zr-MOFs, UiO-68 type MOFs were investigated to photophysical properties through direct solvothermal synthesis with benzotriazole functionalities36. For tetrazole-functionalized Zr-MOFs, the mixed direct synthesis was employed33. These heterocycle-functionalized MOFs could provide potential coordinating sites in MOF pores for catalysis, selective molecular uptake by binding affinity, and energy-related applications, such as proton conduction in fuel cells.

Protocol

The reagents required to prepare MOFs and the ligands are listed in the Table of Materials.

1. Setting up the post-synthetic ligand exchange (PSE) process

  1. Completely dry the pre-synthesized UiO-66 MOFs under vacuum to remove any unreacted metal-salts and ligands in the pores, and remaining solvent residues overnight.
    NOTE: See Supplementary File 1 for the synthesis procedure of UiO-66 MOFs.
  2. Prepare functionalized ligands, H2BDC-Triazole, and H2BDC-Tetrazole (see Supplementary File 1 for the preparation process; Supplementary Figure 1 and Supplementary Figure 2 for characterization) in an isolated state and fully dry under vacuum overnight.
  3. Prepare a 4% potassium hydroxide (KOH) aqueous solution by dissolving potassium hydroxide in deionized water.
  4. Perform the PSE process in 20 mL scintillation vials with polypropylene (PP) caps (see Table of Materials).
  5. Measure the H2BDC-Triazole (23.3 mg, 0.1 mmol) or H2BDC-Tetrazole (23.4 mg, 0.1 mmol) and place into the scintillation vial.
  6. Dissolve the H2BDC ligand in aqueous solution. Use a glass pipette to transfer 1.0 mL of the 4% KOH aqueous solution into the scintillation vial containing BDC-Triazole or BDC-Tetrazole.
    CAUTION: The 4% KOH aqueous solution is highly basic. Avoid all forms of contact and wear personal protective equipment.
  7. Sonicate the mixture until all the solids have fully dissolved.
  8. Neutralize the solution to pH 7. Use a glass pipette to transfer 1 M hydrochloric acid (HCl) aqueous solution with stirring into the scintillation vial containing dicarboxylate until pH 7 is reached. Measure the pH either by pH paper (and its color) or a pH meter.
    NOTE: It is crucial to maintain a pH of 7 during the exchange process, since MOFs are typically unstable under basic conditions (>pH 7), and the BDC ligand is not soluble under acidic conditions (<pH 7). Approximately 1.5 mL of 1 M HCl aqueous solution is required to neutralize BDC-Triazole or BDC-Tetrazole-containing solution.
  9. Add MOFs to the dicarboxylate solution and incubate. Add UiO-66 MOF (33 mg, 0.02 mmol) to the scintillation vial containing pH 7 solution.
    NOTE: At pH 7, UiO-66 MOF particles are not soluble in water, resulting in their suspension in water.
  10. Incubate the scintillation vial containing the MOF and ligand in a shaker at 120 rpm and at room temperature for 24 h.
    ​NOTE: Stirring can be used as an alternative to shaker-incubation for the PSE process. However, caution should be taken, since physical contact between the magnetic stirring bar and MOFs can result in cracking or breaking of the MOF particles.

2. Isolating the exchanged MOF and washing process

  1. After incubation, isolate the solid MOF from the mixture by centrifugation (1,166 x g, 5 min, room temperature).
  2. Add fresh methanol (10 mL) to the obtained solid MOF and shake the mixture to form a heterogeneous mixture to dissolve the remaining unexchanged BDC ligands.
  3. Isolate the solid that was isolated by centrifugation (1,166 x g, 5 min, room temperature).
  4. Repeat steps 2.2-2.3 two more times for a total of three washing cycles.
  5. Fully dry the exchanged MOF solid under a vacuum for overnight after the last washing.

3. Characterization of the MOF by powder x-ray diffraction (PXRD)

  1. Transfer approximately 10 mg of the exchanged MOF solid to a PXRD sample holder (see Table of Materials).
  2. Place the sample holder in the diffractometer.
  3. Collect the PXRD pattern (Figure 2) in the 2θ range from 5° to 30°.
  4. Compare the obtained data to the parent UiO-66 MOF and the simulated pattern.

4. Characterization of the MOF by nuclear magnetic resonance (NMR) after digestion

  1. Transfer approximately 30 mg of the exchanged MOF solid to a fresh 4 mL vial.
  2. Use a micropipette to transfer 400 µL of DMSO-d6 to the MOF sample.
  3. Use a micropipette to transfer 200 µL of 4.14 M NH4F/D2O solution to a DMSO-d6 suspension of MOF powder.
    NOTE: An aqueous solution of approximately 40% HF can be used instead of the NH4F/D2O solution. In this case, a significant H2O peak is observed in the NMR. However, clearer digestion is possible in the case of HF digestion.
    CAUTION: HF is highly toxic to the body and central nervous system. All forms of contact should be avoided, work should be performed in a fume hood, and personal protective equipment should be worn.
  4. Sonicate the heterogeneous mixture for 30 min until the MOF is dissolved in the dimethyl sulfoxide (DMSO)-D2O mixed solvent after digestion.
  5. Remove any remaining insoluble solids by filtering the solution through a polyvinylidene difluoride (PVDF) syringe filter (Φ 13 mm, 0.45 µm pore; see Table of Materials) while transferring it from the 4 mL vial to an NMR tube.
  6. Place the NMR tube in the NMR machine. Collect the NMR data (Figure 3).

Results

The successful synthesis of exchanged UiO-66 MOFs, UiO-66-Triazole, and UiO-66-Tetrazole produced colorless microcrystalline solids. Both H2BDC-Triazole and H2BDC-Tetrazole ligands also exhibited a colorless solid state. The standard method used to determine the success of the exchange involved measuring the PXRD patterns and comparing the crystallinity of the sample with pristine UiO-66 MOF. Figure 2 displays the PXRD patterns of exchanged UiO-66-Triazole and UiO-66-Te...

Discussion

The PSE process with functionalized BDC ligands toward Zr-based UiO-66 MOFs is a simple and versatile method to obtain MOFs with chemical tags. The PSE process is best conducted in aqueous media, requiring the initial step of solvating the ligand in an aqueous medium. When using pre-synthesized BDC with functional groups, direct dissolution in a basic solvent, such as a 4% KOH aqueous solution, is recommended. Alternatively, sodium or potassium salt of benzene-1,4-dicarboxylate may be used. Neutralization to pH 7 is crit...

Disclosures

The authors have nothing to disclose.

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (NRF-2022R1A2C1009706).

Materials

NameCompanyCatalog NumberComments
2-Bromoterephthalic acidBLD PharmBD5695reagent for BDC-Triazole
AzidotrimethylsilaneSimga Aldrich155071reagent for BDC-Triazole
Bis(triphenylphosphine)palladium(II) dichlorideTCIB1667reagent for BDC-Triazole
Copper(I) cyanideAlfa-Aesar12135reagent for BDC-Tetrazole
Copper(I) iodideAcros organics20150reagent for BDC-Triazole
Digital Orbital ShakerDaihan ScientificSHO-1DPSE
Formic AcidDaejung chemicalF0195reagent for BDC-Tetrazole
Hybrid LC/Q-TOF systemBruker BioSciencesmaXis 4GHR-MS
Lithum hydroxide monohydrateDaejung chemical5087-4405reagent for BDC-Triazole
Magnesium sulfateSamchun chemicalM1807reagent for BDC-Triazole
Methyl alcoholDaejung chemicalM0584reagent for BDC-Tetrazole
N,N-DimethylformamideDaejung chemicalD0552reagent for BDC-Tetrazole
Nuclear Magnetic Resonance Spectrometer-500 MHzBrukerAVANCE 500MHzNMR
Polypropylene cap (22 mm, Cork-Backed Foil Lined)Sungho Korea22-200material for digestion
Potassium cyanideAlfa-AesarL13273reagent for BDC-Tetrazole
PVDF Synringe filter (13 mm, 0.45 µm)LK Lab KoreaF14-61-363material for digestion
Scintillation vial (20 mL, borosilicate glass)Sungho Korea74504-20material for digestion
Sodium azide TCIS0489reagent for BDC-Tetrazole
Sodium bicarbonateSamchun chemicalS0343reagent for BDC-Triazole
Tetrabutylammonium fluoride (1 M THF solution)Acros organics20195reagent for BDC-Triazole
TriethylamineTCIT0424reagent for BDC-Triazole
Triethylamine hydrochlorideDaejung chemical8628-4405reagent for BDC-Tetrazole
Trimethylsilyl-acetyleneAlfa-AesarA12856reagent for BDC-Triazole
TriphenylphosphineTCIT0519reagent for BDC-Triazole
X RAY DIFFRACTOMETER SYSTEMRigakuMiniFlex 600PXRD
Zirconium(IV) chlorideAlfa-Aesar12104reagent for BDC-Tetrazole

References

  1. Zhou, H. -. C., Long, J. R., Yaghi, O. M. Introduction to metal-organic frameworks. Chemical Reviews. 112 (2), 673-674 (2012).
  2. Furukawa, H., Cordova, K. E., O'Keefe, M., Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science. 341 (6149), 1230444 (2013).
  3. Razavi, S. A. A., Morsali, A. Linker functionalized metal-organic frameworks. Coordination Chemistry Reviews. 399, 213023 (2019).
  4. Kim, D., Kang, M., Ha, H., Hong, C. S., Kim, M. Multiple functional groups in metal-organic frameworks and their positional regioisomerism. Coordination Chemistry Reviews. 438, 213892 (2021).
  5. Lu, W., et al. Tuning the structure and function of metal-organic frameworks via linker design. Chemical Society Reviews. 43 (16), 5561-5593 (2014).
  6. Xie, L. -. H., Liu, X. -. M., He, T., Li, J. -. R. Metal-organic frameworks for the capture of trace aromatic volatile organic compounds. Chem. 4 (8), 1911-1927 (2018).
  7. Lv, X. -. L., et al. Ligand rigidification for enhancing the stability of metal-organic frameworks. Journal of the American Chemical Society. 141 (26), 10283-10293 (2019).
  8. Robison, L., et al. Transient catenation in a zirconium-based metal-organic framework and its effect on mechanical stability and sorption properties. Journal of the American Chemical Society. 143 (3), 1503-1512 (2021).
  9. He, T., Kong, X. -. J., Li, J. -. R. Chemically stable metal-organic frameworks: rational construction and application expansion. Accounts of Chemical Research. 54 (15), 3083-3094 (2021).
  10. Kalaj, M., Cohen, S. M. Postsynthetic modification: an enabling technology for the advancement of metal-organic frameworks. ACS Central Science. 6 (7), 1046-1057 (2020).
  11. Mandal, S., Natarajan, S., Mani, P., Pankajakshan, A. Post-synthetic modification of metal-organic frameworks toward applications. Advanced Functional Materials. 31 (4), 2006291 (2021).
  12. Wang, Z., Cohen, S. M. Postsynthetic modification of metal-organic frameworks. Chemical Society Reviews. 38 (5), 1315-1329 (2009).
  13. Tanabe, K. K., Cohen, S. M. Postsynthetic modification of metal-organic frameworks-a progress report. Chemical Society Reviews. 40 (2), 498-519 (2011).
  14. Cohen, S. M. Postsynthetic methods for the functionalization of metal-organic frameworks. Chemical Reviews. 112 (2), 970-1000 (2012).
  15. Wang, Z., Cohen, S. M. Postsynthetic covalent modification of a neutral metal−organic framework. Journal of the American Chemical Society. 129 (41), 12368-12369 (2007).
  16. Garibay, S. J., Cohen, S. M. Isoreticular synthesis and modification of frameworks with the UiO-66 topology. Chemical Communications. 46 (41), 7700-7702 (2010).
  17. Kim, M., Cahill, J. F., Fei, H., Prather, K. A., Cohen, S. M. Postsynthetic ligand and cation exchange in robust metal-organic frameworks. Journal of the American Chemical Society. 134 (43), 18082-18088 (2012).
  18. Kim, M., Cahill, J. F., Su, Y., Prather, K. A., Cohen, S. M. Postsynthetic ligand exchange as a route to functionalization of 'inert' metal-organic frameworks. Chemical Science. 3 (1), 126-130 (2012).
  19. Taddei, M., Wakeham, R. J., Koutsianos, A., Andreoli, E., Barron, A. R. Post-synthetic ligand exchange in zirconium-based metal-organic frameworks: beware of the defects. Angewandte Chemie International Edition. 57 (36), 11706-11710 (2018).
  20. Park, H., et al. Defect engineering into metal-organic frameworks for the rapid and sequential installation of functionalities. Inorganic Chemistry. 57 (3), 1040-1047 (2018).
  21. Kim, S., Lee, J., Jeoung, S., Moon, H. R., Kim, M. Surface-deactivated core-shell metal-organic framework by simple ligand exchange for enhanced size discrimination in aerobic oxidation of alcohols. Chemistry-A European Journal. 26 (34), 7568-7572 (2020).
  22. Lee, J., et al. Pore engineering of covalently connected metal-organic framework nanoparticle-mixed-matrix membrane composites for molecular separation. ACS Applied Nano Materials. 3 (9), 9356-9362 (2020).
  23. Karagiaridi, O., Bury, W., Mondloch, J. E., Hupp, J. T., Farha, O. K. Solvent-assisted linker exchange: an alternative to the de synthesis of unattainable metal-organic frameworks. Angewandte Chemie International Edition. 53 (18), 4530-4540 (2014).
  24. Yu, D., et al. A solvent-assisted ligand exchange approach enables metal-organic frameworks with diverse and complex architectures. Nature Communications. 11, 927 (2020).
  25. Lee, S. Y., et al. Design of ultra-thin nanosheet bimetallic NiCo MOF with binary ligand via solvent-assisted ligand exchange (SALE) reaction for high performance supercapacitors. Electrochimica Acta. 451, 142291 (2023).
  26. Liao, W. -. M., et al. Post-synthetic exchange (PSE) of UiO-67 frameworks with Ru/Rh half-sandwich units for visible-light-driven H2 evolution and CO2 reduction. Journal of Materials Chemistry A. 6 (24), 11337-11345 (2018).
  27. Islamoglu, T., et al. Postsynthetic tuning of metal-organic frameworks for targeted applications. Accounts of Chemical Research. 50 (4), 805-813 (2017).
  28. Lee, J., et al. Strategies in metal-organic framework-based catalysts for the aerobic oxidation of alcohols and recent progress. Bulletin of the Korean Chemical Society. 42 (3), 359-368 (2021).
  29. Kalaj, M., Prosser, K. E., Cohen, S. M. Room temperature aqueous synthesis of UiO-66 derivatives via postsynthetic exchange. Dalton Transactions. 49 (26), 8841-8845 (2020).
  30. Deria, P., et al. Beyond post-synthesis modification: evolution of metal-organic frameworks via building block replacement. Chemical Society Reviews. 43 (16), 5896-5912 (2014).
  31. Han, Y., Li, J. -. R., Xie, Y., Guo, G. Substitution reactions in metal-organic frameworks and metal-organic polyhedral. Chemical Society Reviews. 43 (16), 5952-5981 (2014).
  32. Xu, M. -. M., Chen, Q., Xie, L. -. H., Li, J. -. R. Exchange reactions in metal-organic frameworks: New advances. Coordination Chemistry Reviews. 421, 213421 (2020).
  33. Lee, D., et al. Uncoordinated tetrazole ligands in metal-organic frameworks for proton-conductivity studies. Bulletin of the Korean Chemical Society. 43 (7), 912-917 (2022).
  34. Han, B. -. X., Jiang, Y. -. F., Sun, X. -. R., Li, Z. -. F., Li, G. Proton conductive N-heterocyclic metal-organic frameworks. Coordination Chemistry Reviews. 432, 213754 (2021).
  35. Han, Z., Zhao, Y., Peng, J., Gómez-García, C. J. Unusual oxidation of an N-heterocycle ligand in a metal−organic framework. Inorganic Chemistry. 46 (14), 5453-5455 (2007).
  36. Wu, S., et al. Linker engineering toward full-color emission of UiO-68 type metal-organic frameworks. Journal of the American Chemical Society. 143 (28), 10547-10552 (2021).
  37. Hamzah, H. A., et al. Post-synthetic mannich chemistry on metal-organic frameworks: system-specific reactivity and functionality-triggered dissolution. Chemistry-A European Journal. 24 (43), 11094-11102 (2018).
  38. Oozeerally, R., et al. Systematic modification of UiO-66 metal-organic frameworks for glucose conversion into 5-hydroxymethyl furfural in water. ChemCatChem. 13 (10), 2517-2529 (2021).
  39. Hamzah, H. A., Crickmore, T. S., Rixason, D., Burrows, A. D. Post-synthetic modification of zirconium metal-organic frameworks by catalyst-free aza-Michael additions. Dalton Transactions. 47 (41), 14491-14496 (2018).

Reprints and Permissions

Request permission to reuse the text or figures of this JoVE article

Request Permission

Explore More Articles

TriazoleTetrazoleMetal organic Frameworks MOFsPost synthetic Ligand Exchange PSEFunctionalizationCoordination BondsSolid solution ExchangeHeterocycle InstallationZr based MOFUiO 66Chemical TagsCharacterization TechniquesPowder X ray DiffractionNuclear Magnetic Resonance Spectroscopy

This article has been published

Video Coming Soon

JoVE Logo

Privacy

Terms of Use

Policies

Research

Education

ABOUT JoVE

Copyright © 2025 MyJoVE Corporation. All rights reserved