Multicomponent metal-organic frameworks (MOFs) comprise multiple, structurally diverse linkers fixed into an ordered lattice by metal ions or clusters as secondary building units (SBUs). Here, we show how multicomponent MOFs are ideal platforms for engineering materials with high levels of vacancy defects. First, a new type of quaternary MOF that is built up from two neutral, linear ditopic linkers, a 3-fold-symmetric carboxylate ligand, and a dinuclear paddlewheel SBU was synthesized. This MOF, named MUF-32 (MUF = Massey University Framework), is constructed from dabco, 4,4′-bipyridyl (bipy), 4,4′,4″-nitrilotrisbenzoate (ntb), and zinc(II), and it adopts an ith-d topology. The zinc(II) ions and ntb ligand define an underlying [Zn2(ntb)4/3] sublattice (with pto topology) that is "load bearing" and maintains the structural integrity of the framework. On the other hand, the dabco and bipy ligands are "decorative", and high levels of vacancy defects can be introduced by their partial omission or removal. These defects can be generated by direct synthesis or by postsynthetic modification. The framework structure, crystallinity, and porosity are maintained even when vacancy levels of 80% are reached. Defect healing is possible by introducing free ligands in a solvent-assisted process to restore pristine MUF-32. Computational analysis reveals that the mechanical instability of the [Zn2(ntb)4/3] sublattice sets an upper limit on defect levels in this material. Multicomponent Metal-Organic Frameworks as Defect-Tolerant Materials Seok J. Lee, [a] Celine Doussot, [a] Anthony Baux, [a] Lujia Liu, [a] Geoffrey B. Jameson, [a] Christopher Richardson, [b] Joshua J. Pak, [c] Fabien Trousselet, [d] Francois-Xavier Coudert, [d] Supporting Information PlaceholderABSTRACT: Multicomponent metal-organic frameworks (MOFs) comprise multiple, structurally-diverse linkers fixed into an ordered lattice by metal ions or clusters as secondary building units (SBUs). Here, we show how multicomponent MOFs are ideal platforms for engineering materials with high levels of vacancy defects. First, a new type of quaternary MOF that is built up from two neutral, linear ditopic linkers, a threefold-symmetric carboxylate ligand, and a dinuclear paddlewheel SBU was synthesized. This MOF, named MUF-32 (MUF = Massey University Framework), is constructed from dabco, 4,4'-bipyridyl (bipy), 4,4',4''-nitrilotrisbenzoate (ntb) and zinc(II), and it adopts an ith-d topology. The zinc(III) ions and ntb ligand define an underlying [Zn 2 (ntb) 4/3 ] sublattice (with pto topology) that is 'load bearing' and maintains the structural integrity of the framework. On the other hand, the dabco and bipy ligands are 'decorative' and high levels of vacancy defects can be introduced by their omission. These defects can be generated by direct synthesis or by postsynthetic modification. The framework structure, crystallinity and porosity are maintained even when vacancy levels of 80% are reached. Defect healing is possible by introducing free ligands in a s...
The architecture of metal−organic frameworks (MOFs) is intimately related to their functional properties. In this light, methods that control the topology that is produced by the combination of a given metal cluster and organic linker (or set of linkers) are valuable. Previously, it has been established that 4,4′,4″-nitrilotribenzoate (ntb) and benzene-1,4-dicarboxylate (bdc) combine with Zn 4 O clusters to produce [Zn 4 O(ntb)(bdc) 3/2 ] (UMCM-4). Here, we report frameworks with a different architecture are produced when certain, typically bulky, substituents are introduced to the bdc linker. These MOFs are designated as MUF-8, and they adopt the ith-d topology. The general formula of the MUF-8 family is [Zn 4 O(ntb) 4/3 (bdc-X)], where bdc-X is a substituted bdc linker. Frameworks that are isoreticular to UMCM-4, termed the MUF-84 family, were observed when small substituents were appended to the bdc linker. Many MUF-8 and MUF-84 materials are accessible by direct synthesis. To generate frameworks that could not be synthesized directly, postsynthetic exchange reactions of the bdc linkers were employed.
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