Oral Presentation Royal Australian Chemical Institute National Congress 2026

Pyrazole-Carboxylate Functionalised Indium-Based MOFs: Post-Synthetic Metalation and Interpenetration (136949)

Mei Tieng Yong 1 , Christopher J. Sumby 1
  1. Department of Chemistry, School of Physics, Chemistry and Earth Sciences, Adelaide University, Adelaide, SA, Australia

Metal-organic frameworks (MOFs) are highly tunable, porous crystalline materials formed through the coordination-driven self-assembly of organic linkers and metal nodes.1 Through careful ligand design, a vast number of reactive groups and functionalities can be incorporated into the MOF structure to tailor their properties. By incorporating vacant coordination sites into organic linkers, MOFs can undergo post-synthetic metalation (PSMet) with secondary metal species without disrupting the overall framework.2 These MOFs can act as crystalline sponges, enabling single-crystal X-ray analysis of otherwise unstable or reactive metal species.

Our group has shown site isolation and structural elucidation of Rh(I) and Mn(I) complexes in a pyrazole-carboxylate functionalised manganese MOF (MnMOF-1).3, 4 More recently, we developed a series of chemically and thermally stable pyrazole-carboxylate functionalised zirconium MOFs (UAM-1000 series) capable of PSMet with a broad range of mono- and dinuclear metal complexes.5

Here, we report the expansion of the library of chemically and thermally robust flexible MOFs and the synthesis of an indium-based MOF (InMOF-10) with a honeycomb-like stp-topology. This is synthesised from a flexible 4-connected pyrazole-carboxylate linker. SCXRD analysis revealed that InMOF-10 features hexagonal pores with notably large pore diameters of approximately 30 Å and accessible bispyrazole sites that enable PSMet with 4d transition metal complexes. InMOF-10 displays interesting interpenetration behaviour, further contributing to its structural complexity and potential functionality.

  1. H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi, Science, 2013, 341, 1230444.
  2. J. D. Evans, C. J. Sumby and C. J. Doonan, Chem. Soc. Rev., 2014, 43, 5933–5951.
  3. A. Burgun, C. J. Coghlan, D. M. Huang, W. Chen, S. Horike, S. Kitagawa, J. F. Alvino, G. F. Metha, C. J. Sumby and C. J. Doonan, Angew. Chem. Int. Ed., 2017, 56, 8412–8416.
  4. R. J. Young, M. T. Huxley, L. Wu, J. Hart, J. O’Shea, C. J. Doonan, N. R. Champness and C. J. Sumby, Chem. Sci., 2023, 14, 9409–9417.
  5. P. Gimeno-Fonquernie, J. Albalad, J. D. Evans, J. Price, C. J. Doonan and C. J. Sumby, Inorg. Chem., 2023, 62, 19208–19217.