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.