Metal-organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented -OH groups and large 1D mesopores and apertures.

lett.8b00154. Details on experimental and computational methods as well as adsorption isotherms, isosteric heats of adsorption, and PXRD patterns (PDF)■ AUTHOR INFORMATION

An Al(porphyrin) functionalized with a large axial ligand was incorporated into a porous organic polymer (POP) using a cobalt-catalyzed acetylene trimerization strategy. Removal of the axial ligand afforded a microporous POP that is catalytically active in the methanolysis of a nerve agent simulant. Supercritical CO2 processing of the POP dramatically increased the pore size and volume, allowing for significantly higher catalytic activities.

Robust catechol-functionalized porous organic polymers (POPs) with tunable porosities (560−1050 m 2 /g) and degrees of functionalization were synthesized using a cobaltcatalyzed acetylene trimerization (CCAT) strategy. Post-synthesis metalation can be readily carried out with a wide range of metal precursors (Cu II , Mg II , and Mn II salts and complexes), resulting in metalated POPs with enhanced heat of hydrogen adsorptions compared to the starting nonmetalated materials.

Methyl-, hydroxymethyl-, and phthalimidomethyl-functionalized versions of the porous organic polymer PAF-1 have been obtained through de novo synthesis. The CO 2 adsorption capacity of PAF-1-CH 2 NH 2 , obtained through the post-synthesis deprotection of PAF-1-CH 2 -phthalimide, has been shown to exceed that of PAF-1.