Functional Metal–Organic Frameworks via Ligand Doping: Influences of Ligand Charge and Steric Demand

Doping a functional ligand into a known crystalline system built from ligands of similar shape and length provides a powerful strategy to construct functional metal–organic frameworks (MOFs) with desired functionality and structural topology. This mix-and-match approach mimics the widely applied metal ion doping (or solid solution formation) in traditional inorganic materials, such as metal oxides, wherein maintaining charge balance of the doped lattice and ensuring size match between doped metal ions and the parent lattice are key to successful doping. In this work, we prepared three sterically demanding dicarboxylate ligands based on Ir/Ru-phosphors with similar structures and variable charges (−2 to 0), [Ir(ppy)3]-dicarboxylate (L 1 , ppy is 2-phenylpyridine), [Ir(bpy)(ppy)2]+-dicarboxylate (L 2 , bpy is 2,2′-bipyridine), and Ru(bpy)3]2+-dicarboxylate (L 3 ), and successfully doped them into the known IRMOF-9/-10 structures by taking advantage of matching length between 4,4′-biphenyl dicarboxylate (BPDC) and L 1 –L 3 . We systematically investigated the effects of size and charge of the doping ligand on the MOF structures and the ligand doping levels in these MOFs. L 1 carries a −2 charge to satisfy the charge requirement of the parent Zn4O(BPDC)3 framework and can be mixed into the IRMOF-9/-10 structure in the whole range of H2 L 1 /H2BPDC ratios from 0 to 1. The steric bulk of L 1 induces a phase transition from the interpenetrated IRMOF-9 structure to the non-interpenetrated IRMOF-10 counterpart. L 2 and L 3 do not match the dinegative charge of BPDC in order to maintain the charge balance for a neutral IRMOF-9/-10 framework and can only be doped into the IRMOF-9 structure to a certain degree. L 2 and L 3 form a charge-balanced new phase with a neutral framework structure at higher doping levels (>8% For L 2 and >6% For L 3 ). This systematic investigation reveals the influences of steric demand and charge balance on ligand doping in MOFs, a phenomenon that has been well-established in metal ion doping in traditional inorganic materials.