Inter-ligand cross-links determine secondary building unit formation in oligoMOFs

OligoMOFs are a class of metal-organic frameworks (MOFs) that feature ligands covalently cross-linked into oligomers as intrinsic structural components. A recent study has demonstrated that the size and flexibility of the tether moieties can result in the formation of oligoMOFs with different isomeric structures via geometrical distortions in the secondary building unit (SBU). In this work, it is demonstrated that tethered dimeric ligands with slightly different carbon chain lengths can direct the formation of oligoMOFs with SBUs of different structure and nuclearity. Specifically, inter-ligand cross links are used as a sensitive probe of the phase landscape of MOFs with the composition [Zn₂(R-bdc)₂(bpy)] (bdc = 1,4-benzenedicarboxylate, bpy = 4,4'-bipyridine), showing that a hexyl tether results in a framework structure identical to MOF-508, based on dinuclear {Zn₂} "paddlewheel" SBUs, while heptyl and octyl tethers result in a "honeycomb-like" framework structure based on an infinite rod-like Zn²⁺ SBU bridged by carboxylate ligands. These results are the first examples of tether length influencing SBU chemistry in MOFs and help understand the interplay between the MOF lattice and the geometric constraints imposed by inter-ligand cross-links in oligoMOFs.