title: Topological Transformation of a Metal-Organic Framework Triggered by Ligand Exchange.
abstract: Here we describe the topological transformation of the pores of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) 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 dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol %, as determined by solution1H 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.
authors.affiliation: Department of Organic Chemistry and Berzelii Center EXSELENT on Porous Materials, Stockholm University , SE-10691 Stockholm, Sweden.
authors.forename: Greco
authors.initials: G
authors.lastname: González Miera
authors.affiliation: Department of Organic Chemistry and Berzelii Center EXSELENT on Porous Materials, Stockholm University , SE-10691 Stockholm, Sweden.
authors.forename: Antonio
authors.identifier: http://orcid.org/0000-0002-1333-7740
authors.initials: A
authors.lastname: Bermejo Gómez
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Chupas
authors.affiliation: Department of Organic Chemistry and Berzelii Center EXSELENT on Porous Materials, Stockholm University , SE-10691 Stockholm, Sweden.
authors.forename: Belén
authors.identifier: http://orcid.org/0000-0002-7898-317X
authors.initials: B
authors.lastname: Martín-Matute
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Karena W
authors.initials: KW
authors.lastname: Chapman
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Ana E
authors.identifier: http://orcid.org/0000-0002-2248-2739
authors.initials: AE
authors.lastname: Platero-Prats