Functional group tolerance in BTB-based metal–organic frameworks (BTB – benzene-1,3,5-tribenzoate)

•Three derivatives of a trigonal linker were tested in isoreticular MOF synthesis.•Three new isoreticular compounds could be identified.•Two new compounds with differing topology from the parent MOFs could be identified.•The substituents demonstrated great impact on the definite framework topology.

The effect of different substituents on the structural tolerance of benzene-1,3,5-tribenzoate (BTB) based MOFs was studied. For this purpose, three new BTB derivatives ((NH2)3-BTB, tri((tert-butoxycarbonyl)-amino)-BTB; tri((S)-2-acetoxy-2-phenylacetamido)-BTB) were synthesized and utilized in MOF synthesis using synthetic conditions established for eight known MOFs. Three new isoreticular compounds (NH2-DUT-6, NHBoc-DUT-25, mand-DUT-25) could be identified. Furthermore, two compounds with network topologies differing from the parent compound comprising NHBoc-BTB and Cu-paddlewheels as nodes were found: Cu2(H2O)2(H(NHBoc)-BTB)2 (1), a dense structure containing layers with sql topology, and Cu3(H2O)(NHBoc-BTB)2(bipy) (bipy – 4,4′-bipyridine, DUT-109), with crosslinked iab-network. The porosity of DUT-109 was proven by liquid phase adsorption of ethyl cinnamate from n-heptane. In general, a significant influence of the BTB substituent on the framework formation could be demonstrated.

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