title: 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].
authors.affiliation: School of Chemistry &Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, South Australia 5005, Australia.
authors.forename: Witold M
authors.initials: WM
authors.lastname: Bloch
authors.affiliation: School of Chemistry &Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, South Australia 5005, Australia.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Burgun
authors.affiliation: School of Chemistry &Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, South Australia 5005, Australia.
authors.forename: Campbell J
authors.initials: CJ
authors.lastname: Coghlan
authors.affiliation: Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 0200, Australia.
authors.forename: Richmond
authors.initials: R
authors.lastname: Lee
authors.affiliation: Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 0200, Australia.
authors.forename: Michelle L
authors.identifier: 0000000308287053
authors.initials: ML
authors.lastname: Coote
authors.affiliation: School of Chemistry &Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, South Australia 5005, Australia.
authors.forename: Christian J
authors.initials: CJ
authors.lastname: Doonan
authors.affiliation: School of Chemistry &Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, South Australia 5005, Australia.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Sumby