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Aqueous Stability of Zirconium Clusters, Including the Zr(IV) Hexanuclear Hydrolysis Complex [Zr6O4(OH)4(H2O)24]12+, from Density Functional Theory

Cite this: Inorg. Chem. 2021, 60, 20, 15456–15466
Publication Date (Web):October 7, 2021
https://doi.org/10.1021/acs.inorgchem.1c02078
Copyright © 2021 American Chemical Society

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    Abstract

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    Framework materials constitute a broad family of solids that range from zeolites and metal–organic frameworks (MOFs) to coordination polymers. The synthesis of such network structures typically rely on precursor molecular building blocks. As an example, the UiO-66 MOF series is constructed of hexanuclear [Zr6O4(OH)4(CO2)12] cluster nodes and linear carboxylate linkers. Unfortunately, these Zr MOF cluster nodes cannot currently be manufactured in a sustainable way, motivating a search for “green” alternative synthesis methods. Stabilizing the hexanuclear Zr(IV) cluster (i.e., the hexamer, {Zr612+}) without the use of organic ligation would enable the use of environmentally friendly solvents such as water. The Zr(IV) tetranuclear cluster (i.e., the tetramer, {Zr48+}) can be stabilized in solution with or without organic ligands, yet the hexamer has yet to be synthesized without supporting ligands. The reasons why certain zirconium clusters are favored in aqueous solution over others are not well understood. This study reports the relative thermodynamic instability of the hypothetical hexamer {Zr612+} compared to the ubiquitous {Zr48+} tetramer. Density functional theory calculations were performed to obtain the hydrolysis Gibbs free energy of these species and used to construct Zr Pourbaix diagrams that illustrate the effects of electrochemical potential, pH, and Zr(IV) concentration. It was found that the aqueous {Zr612+} hexamer is ∼17.8 kcal/mol less stable than the aqueous {Zr48+} tetramer at pH = 0, V = 0, and [Zr(IV)] = 1 M, which is an energy difference on the order of counterion interactions. Electronic structure analyses were used to explore trends in the highest occupied molecular orbital–lowest unoccupied molecular orbital gap, frontier molecular orbitals, and electrostatic potential distribution of these clusters. The evidence suggests that the aqueous {Zr612+} hexamer may be promoted with more strategic syntheses incorporating minimal ligands and counterions.

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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.inorgchem.1c02078.

    • Zr clusters (ZIP)

    • Structures, bond lengths, and bond angles; hydrolysis Gibbs free energy methods; Pourbaix formalism methods; equilibrium constant methods; energy differences; FMOs; ESP maps; and example input files (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Jon Pascual-Colino, Beñat Artetxe, Garikoitz Beobide, Oscar Castillo, Maria Luz Fidalgo-Mayo, Ainhoa Isla-López, Antonio Luque, Sandra Mena-Gutiérrez, Sonia Pérez-Yáñez. The Chemistry of Zirconium/Carboxylate Clustering Process: Acidic Conditions to Promote Carboxylate-Unsaturated Octahedral Hexamers and Pentanuclear Species. Inorganic Chemistry 2022, 61 (12) , 4842-4851. https://doi.org/10.1021/acs.inorgchem.1c03466
    2. James A. Sommers, Lauren Palys, Nicolas P. Martin, Dylan B. Fast, Mehran Amiri, May Nyman. Oxo-Cluster-Based Zr/HfIV Separation: Shedding Light on a 70-Year-Old Process. Journal of the American Chemical Society 2022, 144 (6) , 2816-2824. https://doi.org/10.1021/jacs.1c13338
    3. Junai Lv, Qi Li, Xin Guan, Na Lin, Jian Zhang, Zhitai Jia, Xutang Tao. Shedding light on intrinsic characteristics and optical properties of novel selenite and tellurite crystals ZrSe 2 O 6 , HfSe 2 O 6 and HfTe 3 O 8. CrystEngComm 2023, 25 (11) , 1675-1682. https://doi.org/10.1039/D2CE01627C

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