The process of Linker insertion into a Zirconium based MOF with bcu topology

Abstract

The synthesis of metal-organic frameworks (MOFs) that contain mixed heterolinker ligands of different lengths is very important for the modulation and the tune of the framework properties. Despite tremendous endeavor, it is still very difficult to synthesize a new Zr-based MOF with mixed heterolinker ligands. Recently, preparations of a series of new Zr-MOFs of 10-, 11- and 12-connectivity that contain mixed heterolinker ligands are reported via sequential insertions of additional linkers into a Zr-MOF of 8-connectivity composed of relatively flexible ligand, dimethyl 2,2'-dimethylbiphenyl-4,4'-dicarboxylic acid (H2Me2-BPDC) having dihedral angle of biphenyl rings.1 Here we report the preparation of a new Zr-MOF of 8-connectivity with rigid 2,6-naphthalene dicarboxylic acid (H2NDC) and preparations of a series of new Zr-based MOF of 12-connectivity that contain NDC and functionalized 1,4-benzenedicarboxylate via additional linker insertion. Through single crystal X-ray diffraction, the processes of additional insertion of ligands can be confirmed.