Architectural Diversity in Multicomponent Metal–Organic Frameworks Constructed from Similar Building Blocks

Abstract

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.

Catalysts Confined in Programmed Framework Pores Enable New Transformations and Tune Reaction Efficiency and Selectivity

“…Porosity − is the most important feature of metal–organic frameworks (MOFs), and the diversification of pore spaces encompasses opportunities to optimize functional attributes. − Metal–organic frameworks have found a niche as heterogeneous catalysts. − Research in this domain has been facilitated by modern synthetic organic protocols, which offer routes to functionalized ligands and thus pore environments with tailored characteristics. This is particularly relevant to multicomponent metal–organic frameworks, which are built up from a set of two or three ligands with different geometries. − Isoreticular series of frameworks emerge from certain sets of ligands in which the members bear different functional groups. This constitutes a method for obtaining pores that can be programmed by the size and chemical characteristics of the functional groups installed on the linkers.…”

Modulating the Performance of an Asymmetric Organocatalyst by Tuning Its Spatial Environment in a Metal–Organic Framework

“…Although such materials can exhibit interesting functional properties, , the linkers are distributed in the lattice with a degree of randomness, which leads to pore heterogeneity. − This will frequently be a disadvantage for applications such as catalysis and sensing, which benefit from architectural regularity. An alternative strategy of using two − or three ,− topologically distinct linkers to build up multicomponent MOFs can preserve pore homogeneity. Since the linkers can be discriminated during framework assembly, they become positioned in unique lattice sites.…”

Isoreticular chemistry of scandium analogues of the multicomponent metal–organic framework MIL-142

“…The MIL-142(Sc) series is the first reported instance of multicomponent Sc MOFs that contain geometrically-distinct linkers (see Table ST6 for other multicomponent MOFs). [48][49][50][51] Furthermore, MIL-142(Sc) permits the substitution of both di-and tricarboxylate linkers in addition to the dicarboxylate substitution already reported for the Fe form.…”