Route to a Family of Robust, Non‐interpenetrated Metal–Organic Frameworks with pto‐like Topology

Abstract A combination of topological rules and quantum chemical calculations has facilitated the development of a rational metal–organic framework (MOF) synthetic strategy using the tritopic benzene‐1,3,5‐tribenzoate (btb) linker and a neutral cross‐linker 4,4′‐bipyridine (bipy). A series of new compounds, namely [M 2 (bipy)] 3 (btb) 4 (DUT‐23(M), M=Zn, Co, Cu, Ni), [Cu 2 (bisqui) 0.5 ] 3 (btb) 4 (DUT‐24, bisqui=diethyl ( R , S )‐4,4′‐biquinoline‐3,3′‐dicarboxylate), [Cu 2 (py) 1.5 (H 2 O) 0.5 ] 3 (btb) 4 (DUT‐33, py=pyridine), and [Cu 2 (H 2 O) 2 ] 3 (btb) 4 (DUT‐34), with high specific surface areas and pore volumes (up to 2.03 m 3 g −1 for DUT‐23(Co)) were synthesized. For DUT‐23(Co), excess storage capacities were determined for methane (268 mg g −1 at 100 bar and 298 K), hydrogen (74 mg g −1 at 40 bar and 77 K), and n ‐butane (99 mg g −1 at 293 K). DUT‐34 is a non‐cross‐linked version of DUT‐23 (non‐interpenetrated pendant to MOF‐14) that possesses open metal sites and can therefore be used as a catalyst. The accessibility of the pores in DUT‐34 to potential substrate molecules was proven by liquid phase adsorption. By exchanging the N,N donor 4,4′‐bipyridine with a substituted racemic biquinoline, DUT‐24 was obtained. This opens a route to the synthesis of a chiral compound, which could be interesting for enantioselective separation.