Covalent Organic Framework (COF‐1) under High Pressure

Abstract COF‐1 has a structure with rigid 2D layers composed of benzene and B 3 O 3 rings and weak van der Waals bonding between the layers. The as‐synthesized COF‐1 structure contains pores occupied by solvent molecules. A high surface area empty‐pore structure is obtained after vacuum annealing. High‐pressure XRD and Raman experiments with mesitylene‐filled (COF‐1‐M) and empty‐pore COF‐1 demonstrate partial amorphization and collapse of the framework structure above 12–15 GPa. The ambient pressure structure of COF‐1‐M can be reversibly recovered after compression up to 10–15 GPa. Remarkable stability of highly porous COF‐1 structure at pressures at least up to 10 GPa is found even for the empty‐pore structure. The bulk modulus of the COF‐1 structure (11.2(5) GPa) and linear incompressibilities ( k [100] =111(5) GPa, k [001] =15.0(5) GPa) were evaluated from the analysis of XRD data and cross‐checked against first‐principles calculations.