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Clickable Norbornene-Based Zirconium Carboxylate Polyhedra

Cite this: Chem. Mater. 2023, 35, 4, 1651–1658
Publication Date (Web):February 13, 2023
https://doi.org/10.1021/acs.chemmater.2c03252
Copyright © 2023 American Chemical Society

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    Abstract

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    A common way to modify the properties of metal–organic polyhedra (MOPs) is to install pendant functionalities on the organic bridging ligands. These groups can then participate in coupling reactions to further decorate a given architecture. Via exploitation of click chemistry, it is possible to access a diverse library of MOPs that share a common core, which can reduce both synthetic complexity and cost. Herein, we report the formation of a reactive norbornene-based MOP through a one-pot tandem coordination-driven self-assembly/Diels–Alder reaction between fumaric acid and zirconocene dichloride (Cp2ZrCl2). The generality of this tandem process was illustrated by the subsequent synthesis of a norbornene-based Zr cluster formed from maleic acid and Cp2ZrCl2. We demonstrate post-assembly modification of this cage using versatile thiol–ene click chemistry, resulting in the formation of either individual functionalized MOPs or cross-linked polymer/MOP hybrid composites. The physical properties of these composites can be controlled by the addition of poly(ethylene glycol) diacrylate as a co-monomer, allowing for the synthesis of free-standing, flexible films at MOP loadings of 30–60% (w/w). These results demonstrate the effectiveness of thiol–ene click chemistry as a method of MOP functionalization, expanding the toolbox for the synthesis of new advanced materials.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.2c03252.

    • 1H NMR and FTIR spectra, HRMS data, crystallographic details, swelling/sol–gel analysis details, and nitrogen adsorption measurements (PDF)

    • Crystallographic data for [Zr-mal]Cl (CIF)

    • Crystallographic data for corrected [ZrMOP-nor]Cl2 from a previous report (CIF)

    • Crystallographic data for [ZrMOP-nor]Cl2 collected at 293 K (CIF)

    • Crystallographic data for [ZrMOP-nor]Cl2 collected at 90 K from reaction at 60°C (CIF)

    • Crystallographic data for [ZrMOP-nor]Cl2 collected at 90 K from reaction at room temperature (CIF)

    • Crystallographic data for [ZrMOP-stil]Cl2 (CIF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 2 publications.

    1. Heshali K. Welgama, Anish Avasthi, Timothy R. Cook. Metal–Organic Polyhedra and Metal–Organic Frameworks: Understanding How Discrete Versus Extended Structure Impacts Surface Areas and Pore Size Distributions. Chemistry of Materials 2024, 36 (9) , 4185-4195. https://doi.org/10.1021/acs.chemmater.3c03020
    2. Meghan G. Sullivan, Heshali K. Welgama, Matthew R. Crawley, Alan E. Friedman, Timothy R. Cook. Phase-Pure Zirconium Metal–Organic Polyhedra Enabled by a Ligand Substitution Strategy. Chemistry of Materials 2024, 36 (1) , 567-574. https://doi.org/10.1021/acs.chemmater.3c02775

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