Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange

Here we describe the topological transformation of the pores of a new framework in the bio-MOF-100 family (<b>dia-c</b>) into the known isomer (<b>lcs</b>) by doubling the pore volume, which occurs during postsynthesis modifications. During this transformation, reassembling of the metal–organic framework (MOF) building blocks into a completely different framework occurs, involving breaking/forming of metal–ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange to the topological change. Following this method and starting from the pristine dense <b>dia-c</b> phase, open <b>lcs-</b>bio-MOF-100 was prepared and functionalized in situ with an iridium complex (IrL). Alternatively, the <b>dia-c</b> MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol %, as determined by solution ¹H NMR spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer transformation. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. Ligand exchanges occurred quantitatively at room temperature, with no need of excess of the iridium metallolinker