Utilization of a Mixed-Ligand Strategy to Tune the Properties of Cuboctahedral Porous Coordination Cages.

Ligand functionalization has been thoroughly leveraged to alter the properties of paddlewheel-based coordination cages where, in the case of ligand-terminated cages, functional groups are positioned on the periphery of synthesized cages. While these groups can be used to optimize solubility, porosity, crystal packing, thermal stability toward desolvation, reactivity, or optical activity, optimization of multiple properties can be challenging given their interconnected nature. For example, installation of functional groups to increase the solubility of porous cages typically has the effect of decreasing their porosity and stability toward thermal activation.

Structural effects on the bromination rate and selectivity of alkylbenzenes and alkoxybenzenes in aqueous solution.

Aqueous free bromine species (e.g., HOBr, BrCl, Br2, BrOCl, Br2O, and H2OBr+) can react with activated aromatic compounds via electrophilic aromatic substitution to generate products with industrial applications, environmental consequences, and potentially adverse biological effects.

Using Low-Pressure Methane Adsorption Isotherms for Higher-Throughput Screening of Methane Storage Materials.

A useful correlation between the low-pressure (up to 1.2 bar), low-temperature (195 K) and high-pressure (up to 65 bar), room temperature (298 K) methane storage properties of a range of porous materials is reported. Methane isotherms under these two sets of conditions show a remarkable agreement in both equilibrium adsorption and deliverable capacities for materials with pore volumes that are less than approximately 0.

Synthesis and characterization of low-nuclearity lantern-type porous coordination cages.

Permanent porosity in lantern-type ML paddlewheel-based cages is rare and has only been reported for naphthalene, naphthyridine, and diethynylbenzene-based linkers. This work presents the design, synthesis, and characterization of small lanterns that exhibit CO accessible BET surface areas in excess of 200 m g. The crystal packing and porosity of these cages can be tuned by either ligand functionalization or the choice of M source used in their synthesis.

Tuning the Porosity, Solubility, and Gas-Storage Properties of Cuboctahedral Coordination Cages via Amide or Ester Functionalization.

The molecular nature of porous coordination cages can endow these materials with significant advantages as compared to extended network solids. Chiefly among these is their solubility in volatile solvents, which can be leveraged in the synthesis, characterization, modification, and utilization of these adsorbents. Although cuboctahedral, paddlewheel-based coordination cages have shown some of the highest surface areas for coordination cages, they often have limited solubility.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization.

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc) . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru and Cu sites housed within [M L ] phases.