Hybrid Single‐Crystalline Mesoporous Frameworks Merging Metal–Organic and Hydrogen‐Bonded Organic Networks

ABSTRACT Mesoporous materials represent an important class of porous materials; however, it remains a great challenge to systematically synthesize hybrid single‐crystalline mesoporous frameworks merging metal–organic and hydrogen‐bonded organic networks. Herein, we report a hybrid merged‐net strategy that integrates a supramolecular hydrogen‐bonded organic network with a single‐crystalline mesoporous metal–organic framework (MOF), significantly enhancing structural robustness without sacrificing intrinsic mesoporosity. The assembly of pyridine‐containing carboxylate linkers and iron‐containing trinuclear clusters affords M‐PPB featuring the (6,6)‐connected 6 2 T44 net, in which directional O─H⋯N hydrogen bonds between adjacent linkers form a one‐dimensional hydrogen‐bonded network. In contrast to the unstable parent (4,6)‐connected stp ‐MOF, M‐PPB—merging metal–organic and hydrogen‐bonded organic networks—exhibits enhanced robustness and achieves full porosity, displaying a pore volume of 1.58 cm 3 g − 1 . We further apply an isoreticular expansion strategy to synthesize extended MOFs—M‐PPPB—containing mesopores of about 4.2 nm and exhibiting a pore volume of up to 2.77 cm 3 g − 1 . On account of its ultrahigh porosity, M‐PPPB exhibits a methane uptake of 1.047 g g − 1 at 159 K and 10 bar, nearly twice that of M‐PPB, while its hydrogen uptake at 77 K and 100 bar increases by about 50%.