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Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange

Published: June 23rd, 2023



1Department of Chemistry, Chungbuk National University, 2Department of Chemistry Education, Seoul National University
* These authors contributed equally

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.

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.

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 wi....

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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 l.......

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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.......

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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.......

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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).


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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
Zirconium(IV) chlorideAlfa-Aesar12104reagent for BDC-Tetrazole

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