Solitary Medium of a Multifunctional Ionic Liquid for Crystallizing Hierarchically Porous Metal-Organic Frameworks.

Hierarchically porous metal-organic frameworks (HP-MOFs), dominating both the micro- and mesoporous regimes, show high potentials in various applications especially those involving bulky biomolecules. The templating method has been proven to be effective in the fabrication of HP-MOFs; however, complicated synthetic systems containing solvents, templates, and additives are frequently employed. Here we report the first example of designing a poly(ethylene glycol)-based alkylammonium and bromide multifunctional ionic liquid (IL) as a solitary medium to construct HP-MOFs, avoiding the involvement of any additional media. Besides the ready solubilization of MOF precursors in the multifunctional IL due to a poly(ethylene glycol) chain as the solubilizer, the ionic moiety facilitates electrostatic interaction to create a templating effect. Hence, UiO-66 with hierarchical porosity has been successfully fabricated, and such a methodology can also be applied to the construction of other HP-MOFs. The resultant HP-UiO-66 is efficient in the encapsulation of bulky biomolecule cytochrome c, and the adsorption capacity is obviously superior to that of the microporous counterpart.