Molecular assemblies based on homobimetallic paddlewheel units bridged by carboxylate containing ligands are commonplace within the porous materials community. These materials have been synthesized as 3-dimensional frameworks, 2-dimensional sheets, and less commonly as zero-dimensional discrete cages. Discrete cages containing transition metal cations with coordinatively-unsaturated sites remain a challenging target in the synthesis of porous molecules. Discrete porous molecules represent a significant fraction of porous materials and have found utility in a wide variety of applications from gas separation, catalysis, sensing, and notably incorporation into the first permanently porous liquid. As compared to three-dimensional porous materials, including MOFs, COFs, activated carbons, and zeolites or two-dimensional sheets, porous molecules offer the potential benefit of solubility. Whereas carboxylate containing metal-organic frameworks have been reported for nearly every transition metal and a variety of main group metals, discrete cages have been limited to Cr, Cu, Mo, Rh, and Ru for carboxylate-based materials. Efforts thus far have been focused on the synthesis of discrete assemblies utilizing other first row transition metals. Herein, we report the design and synthesis of three porous hybrid inorganic/organic molecular assemblies based on cobalt(II) and nickel(II). Precise tuning of ligand functionalization allows for the isolation of molecular species in addition to two- and three-dimensional metal-organic frameworks. The cobaltous and nickelous cage compounds display excellent thermal stability up to 200 °C and moderate BET surface areas. The design and synthesis of these materials will be discussed.<br/>

Design, synthesis, and characterization of novel porous coordination complexes

256th National Meeting (2018)

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