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Article Abstract
Porous coordination cages (PCCs), molecular analogs of metal-organic frameworks, offer modular platforms for studying the adsorption properties of small molecules, with coordinatively unsaturated metal centers playing a pivotal role in tuning these behaviors. In this work, we present the synthesis, activation, and detailed gas adsorption studies of second-row transition metal-based ML cuboctahedral cages, specifically Mo(bdc), Rh(bdc), and [Ru(bdc)]Cl. These materials represent rare examples of Mo-, Rh-, and Ru-based hybrid porous solids. The synthesis and activation of these cages were optimized to maximize porosity, yielding BET surface areas of up to 832 m/g. Gas adsorption studies with CO and CO reveal distinctive uptake behaviors linked to the metal cations, with Mo(bdc) demonstrating the highest gravimetric CO uptake (2.12 mmol/g at 298 K) and [Ru(bdc)]Cl exhibiting the strongest CO binding (-75 kJ/mol). Additionally, we explore the selective adsorption of unsaturated hydrocarbons, such as ethylene and propylene, revealing strong binding interactions at low pressures as a result of strong metal-hydrocarbon interactions based on pi-backbonding interactions.
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| http://dx.doi.org/10.1021/acs.inorgchem.4c03846 | DOI Listing |
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