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Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks

Abstract

Post-synthetic metallation is employed strategically to imbue metal–organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2][Rh(CO)2Cl2].

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Figure 1: Synthesis and structural representations of MOF 1.
Figure 2: Representations of the dramatic structural flexibility displayed by 1.
Figure 3: Data from the N2 gas adsorption isotherm experiments performed at 77 K for 1-des and 1·[CoCl2].
Figure 4: Structural details of the reversible SC–SC Oh to Td transformation for 1·[Co(H2O)4]Cl2 that can be realized by heating or immersion in acetonitrile.
Figure 5: Reaction scheme showing X-ray crystallographic snapshots along the a axis of 1 treated with [Rh(CO)2Cl]2 and subsequent oxidative reactions.

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Acknowledgements

C.J.D. and C.J.S. acknowledge the Science and Industry Endowment Fund for financial support and the Australian Research Council for funding Future Fellowships (FT100100400 and FT0991910). Aspects of this research were undertaken on the MX1 and MX2 beamlines at the Australian Synchrotron, Victoria, Australia. M.L.C. acknowledges generous allocations of supercomputing time on the National Facility of the National Computational Infrastructure and an ARC Future Fellowship (FT100100320). Correspondence and requests for materials should be addressed to C.J.D. and C.J.S.

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Authors and Affiliations

Authors

Contributions

All authors contributed extensively to the work presented in this paper. W.M.B. and A.B. undertook most of the synthetic work and analysis. C.J.C. measured and interpreted the ICP-MS data. W.M.B., A.B., C.J.C. and C.J.S. collected, solved and refined the SCXRD data. R.L. and M.L.C. undertook the computational studies. W.M.B., C.J.D. and C.J.S. wrote the manuscript with input from the other authors.

Corresponding authors

Correspondence to Christian J. Doonan or Christopher J. Sumby.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2999 kb)

Supplementary information

Crystallographic data for compound 1-des (CIF 32 kb)

Supplementary information

Crystallographic data for compound 1.[Co(H2O)4]Cl2 (CIF 6735 kb)

Supplementary information

Crystallographic data for compound 1.[CoCl2] (CIF 32894 kb)

Supplementary information

Crystallographic data for compound 1.[Rh(CO)2][RhCl2(CO)2] (CIF 36 kb)

Supplementary information

Crystallographic data for compound 1.[Rh(H2O)4]Cl3 (CIF 35 kb)

Supplementary information

Crystallographic data for compound 1.[Rh(COMe)(CO)(CH3CN)I]I (CIF 4420 kb)

Supplementary information

Crystallographic data for compound 1.DMF (CIF 53 kb)

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Bloch, W., Burgun, A., Coghlan, C. et al. Capturing snapshots of post-synthetic metallation chemistry in metal–organic frameworks. Nature Chem 6, 906–912 (2014). https://doi.org/10.1038/nchem.2045

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