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

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) ate valuable. Previously, it has been established that 4,4',4 ''-nitrilotribenzciate (ntb) and benzene-1,4-dicarboxylate (bdc) combine with Zn4O clusters to produce [Zn4O(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 [Zn4O(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.