Issue 7, 2024

Topological analysis and control of post-synthetic metalation sites in Zr-based metal–organic frameworks

Abstract

The design criteria needed for the formation of the sqc metal–organic framework (MOF) topology, from an 8-connecting node and a 4-connecting linker, are unclear due to a limited number of reports. After recently reporting the MOF UAM-1000 (UAM = University of Adelaide Material), which has this rare sqc topology, we present a study that explores the effect of flexible tetrapyrazole carboxylate linker structure metrics on the topology of Zirconium-based MOFs (Zr-MOFs). By modifying the linker length and width, three new Zr-MOFs (UAM-10, UAM-11, and UAM-1002) were synthesized and characterized. The study reveals that linker dimensions influence the accessible conformations, and along with fine-tuning of synthetic conditions, allow control over MOF topology. Additionally, linker flexibility plays a crucial role in the formation of the sqc over the more common csq topology. Finally, the presence of free bis-pyrazolyl groups in the reported MOFs allowed us to evaluate the potential for post-synthetic metalation (PSMet). UAM-10 and UAM-11 are too rigid, the pyrazole groups lack the appropriate arrangement and therefore these materials do not undergo PSMet. In contrast, UAM-1002 with its scu topology exhibits the right quanta of flexibility needed for successful PSMet, making it a promising platform for studying the chemistry of anchored organometallic complexes. Moreover, the different topology for UAM-1002 versus UAM-1000 changes the nature of the PSMet site (bidentate versus a tetradentate site) despite these being made from the same node and linker building blocks.

Graphical abstract: Topological analysis and control of post-synthetic metalation sites in Zr-based metal–organic frameworks

Supplementary files

Article information

Article type
Paper
Submitted
05 Oct 2023
Accepted
21 Dec 2023
First published
22 Dec 2023

J. Mater. Chem. C, 2024,12, 2359-2369

Topological analysis and control of post-synthetic metalation sites in Zr-based metal–organic frameworks

P. Gimeno-Fonquernie, J. Albalad, J. R. Price, W. M. Bloch, J. D. Evans, C. J. Doonan and C. J. Sumby, J. Mater. Chem. C, 2024, 12, 2359 DOI: 10.1039/D3TC03606E

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