Metal–Organic Frameworks with Internal Urea-Functionalized Dicarboxylate Linkers for SO₂ and NH₃ Adsorption

Introduction of a urea R–NH–CO–NH–R group as a seven-membered diazepine ring at the center of 4,4′-biphenyl-dicarboxylic acid leads to a urea-functionalized dicarboxylate linker (L1 2– ) from which four zinc metal–organic frameworks (MOFs) could be obtained, having a {Zn 4 (μ 4 -O)(O 2 C−) 6 } SBU and IRMOF-9 topology (compound [Zn 4 (μ 4 -O)(L1) 3 ], 1, from dimethylformamide, DMF) or a {Zn 2 (O 2 C−) 4 } paddle-wheel SBU in a 2D-network (compound [Zn 2 (L1) 2 (DEF) 2 ·2.5DEF], 2, from diethylformamide, DEF). Pillaring of the 2D-network of 2 with 4,4′-bipyridine (bipy) or 1,2-bis(4-pyridyl)ethane (bpe) gives 3D frameworks with rhombohedrally distorted pcu-a topologies ([Zn 2 (L1) 2 (bipy)], 3 and [Zn 2 (L1) 2 (bpe)], 4, respectively). The 3D-frameworks 1, 3, and 4 are 2-fold interpenetrated with ∼50% solvent-accessible volume, albeit of apparently dynamic porous character, such that N 2 adsorption at 77 K does not occur, while H 2 at 77 K (up to ∼1 wt %) and CO 2 at 293 K (∼5 wt %) are adsorbed with large hystereses in these flexible MOFs. The urea-functionalized MOF 3 exhibits an uptake of 10.9 mmol g –1 (41 wt %) of SO 2 at 293 K, 1 bar, which appears to be the highest value observed so far. Compounds 3 and 4 adsorb 14.3 mmol g –1 (20 wt %) and 17.8 mmol g –1 (23 wt %) NH 3, respectively, which is at the top of the reported values. These high uptake values are traced to the urea functionality and its hydrogen-bonding interactions to the adsorbents. The gas uptake capacities follow the specific porosity of the frameworks, in combination with pore aperture size and affinity constants from fits of the adsorption isotherms.