Covalent Organic Framework (COF-1) under High Pressure

COF-1 has a structure with rigid 2D layers composed of benzene and B₃O₃ 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.