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Updated: Feb 24, 2026

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Transformation of Metal-Organic Framework Secondary Building Units into Hexanuclear Zr-Alkyl Catalysts for Ethylene
Pengfei Ji1, Joseph B Solomon1, Zekai Lin1
1Department of Chemistry, The University of Chicago , 929 E 57th Street, Chicago, Illinois 60637, United States.
Abstract:
We report the stepwise and quantitative transformation of the Zr6(μ3-O)4(μ3-OH)4(HCO2)6 nodes in Zr-BTC (MOF-808) to the [Zr6(μ3-O)4(μ3-OH)4Cl12]6- nodes in ZrCl2-BTC, and then to the organometallic [Zr6(μ3-O)4(μ3-OLi)4R12]6- nodes in ZrR2-BTC (R = CH2SiMe3 or Me). Activation of ZrCl2-BTC with MMAO-12 generates ZrMe-BTC, which is an efficient catalyst for ethylene polymerization. ZrMe-BTC displays unusual electronic and steric properties compared to homogeneous Zr catalysts, possesses multimetallic active sites, and produces high-molecular-weight linear polyethylene. Metal-organic framework nodes can thus be directly transformed into novel single-site solid organometallic catalysts without homogeneous analogs for polymerization reactions.
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