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 m2/g, pore apertures up to 2.4 nm, with record CO2 and C2H2 adsorption capacities for HOFs at 195 K. One-pot incorporation of AgOTf during mechanosynthesis enables programmable pore decoration, enhancing room-temperature C2H2 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.