A Modular Tecton Matrix for Mechanosynthesis of Large‐Pore Hydrogen‐Bonded Organic Frameworks With Programmable Pore Environments

Hydrogen‐bonded organic frameworks (HOFs) offer versatile porous architectures, yet predictable pore expansion via tecton extension remains challenging because framework assembly is highly sensitive to solvent‐mediated crystallization. Here, we establish a mechanosynthesis‐enabled modular tecton matrix for constructing large‐pore HOFs. Pairwise combination of complementary tectons systematically generates four micro‐ and mesoporous HOFs, including G4, which is difficult to obtain by solution crystallization. These HOFs exhibit surface areas up to 1824 m 2 /g, pore apertures up to 2.4 nm, with record CO 2 and C 2 H 2 adsorption capacities for HOFs at 195 K. One‐pot incorporation of AgOTf during mechanosynthesis enables programmable pore decoration, enhancing room‐temperature C 2 H 2 uptake through stronger framework‐substrate interactions. This work establishes a modular tecton matrix enabled by mechanosynthesis as a general design and discovery strategy for constructing and functionalizing large‐pore HOFs.