Selective CO2 Sorption Using Compartmentalized Coordination Polymers with Discrete Voids*.

Carbon capture and storage with porous materials is one of the most promising technologies to minimize CO2 release into the atmosphere. Here, we report a family of compartmentalized coordination polymers (CCPs) capable of capturing gas molecules in a selective manner based on two novel tetrazole-based ligands. Crystal structures have been modelled theoretically under the Density Functional Theory (DFT) revealing the presence of discrete voids of 380 Å3 . Single gas adsorption isotherms of N2 , CH4 and CO2 have been measured, obtaining a loading capacity of 0.6, 1.7 and 2.2 molecules/void at 10 bar and at 298 K for the best performing material. Moreover, they present excellent selectivity and regenerability for CO2 in mixtures with CH4 and N2 in comparison with other reported materials, as evidenced by dynamic breakthrough gas experiments. These frameworks are therefore great candidates for separation of gas mixtures in the chemical engineering industry.

Multivariate sodalite zeolitic imidazolate frameworks: a direct solvent-free synthesis.

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology. In particular, the versatility of this method is demonstrated with three different metal centres (Zn, Co and Fe) and binary combinations of three different ligands (2-methylimidazole, 2-ethylimidazole and 2-methylbenzimidazole). One combination of ligands, 2-ethylimidazole and 2-methylbenzimidazole, results in the formation of SOD frameworks for the three metal centres despite this topology not being obtained for the individual ligands. Theoretical calculations confirm that this topology is the lowest in energy upon ligand mixing.

Heterometallic palladium-iron metal-organic framework as a highly active catalyst for cross-coupling reactions.

Palladium-based metal-organic frameworks (Pd-MOFs) are an emerging class of heterogeneous catalysts extremely challenging to achieve due to the facile leaching of palladium and its tendency to be reduced. Herein, Pd(ii) was successfully incorporated in the framework of a MOF denoted as MUV-22 using a solvent assisted reaction. This stable MOF, with square-octahedron (soc) topology as MIL-127, and a porosity of 710 m2 g-1, is highly active, selective, and recyclable for the Suzuki-Miyaura allylation of aryl and alkyl boronates as exemplified with the coupling between cinnamyl bromide and Me-Bpin, a typically reluctant reagent in cross-coupling reactions.