The unique applications of porous metal–organic framework (MOF) liquids with permanent porosity and fluidity have attracted significant attention. However, fabrication of porous MOF liquids remains challenging because of the easy intermolecular self‐filling of the cavity or the rapid settlement of porous hosts in hindered solvents that cannot enter their pores. Herein, we report a facile strategy for the fabrication of a MOF liquid (Im‐UiO‐PL) by surface ionization of an imidazolium‐functionalized framework with a sterically hindered poly(ethylene glycol) sulfonate (PEGS) canopy. The Im‐UiO‐PL obtained in this way has a CO2 adsorption approximately 14 times larger than that of pure PEGS. Distinct from a porous MOF solid counterpart, the stored CO2 in Im‐UiO‐PL can be slowly released and efficiently utilized to synthesize cyclic carbonates in the atmosphere. This is the first example of the use of a porous MOF liquid as a CO2 storage material for catalysis. It offers a new method for the fabrication of unique porous liquid MOFs with functional behaviors in various fields of gas adsorption and catalysis.

Metal N − heterocyclic carbenes (M − NHCs) on the pore walls of a porous metal − organic framework (MOF) can be used as active sites for efficient organic catalysis. Traditional approaches that need strong alkaline reagents or insoluble Ag2O are not however suitable for the incorporation of NHCs on the backbones of MOFs because such reagents could destroy their frameworks or result in low reactivity. Accordingly, development is needed of facile strategies toward functional MOFs with covalently bound M − NHCs for catalysis. Herein, we describe the development of a general and facile approach to prepare MOFs with covalently linked active M − NHC (M = Pd, Ir) single site catalysts by using a soluble Ag salt AgOC(CF3)3 as the source and subsequent transmetalation. The well − defined M − NHC − MOF (M = Pd, Ir) catalysts obtained in this way have shown excellent catalytic activity and stability in Suzuki reactions and transfer hydrogenation reactions. This provides a general and facile strategy to anchor functional M − NHC single − site catalysts onto functionalized MOFs for different reactions.