RESUMO
Chemically and thermally stable permanently porous coordination cages are appealing candidates for separations, catalysis, and as the porous component of new porous liquids. However, many of these applications have not turned to microporous cages as a result of their poor solubility and thermal or hydrolytic stability. Here we describe the design and modular synthesis of iron and cobalt cages where the carboxylate groups of the bridging ligands of well-known calixarene capped coordination cages have been replaced with more basic triazole units. The resultingly higher M-L bond strengths afford highly stable cages that are amenable to modular synthetic approaches and potential functionalization or modification. Owing to the robust nature of these cages, they are highly processable and are isolable in various physical states with tunable porosity depending on the solvation methods used. As the structural integrity of the cages is maintained upon high activation temperatures, apparent losses in porosity can be mediated by resolvation and crystallization or precipitation.
RESUMO
Enormous efforts have been made to convert biomass to liquid fuels and products catalytically. Long molecules with a suitable structure are ideal precursors for fuels and value-added products. Here, a C21 oxygenate was synthesized for the first time in one step through aldol condensation of furfural and acetone over the amine-functionalized zirconium-based metal-organic framework (MOF), UiO-66-NH2. Structural changes of UiO-66-NH2 were investigated to improve the yield and evaluate the role of the ligand, cluster node, defectiveness, modulator, surface area, and textural properties on the product distribution. We demonstrate the possibility of making long-chain oxygenates without using vegetable oil-derived fatty acids toward 100% waste biomass-derived renewable fuels, lubricants, and surfactants.
