Geomimetic Hydrothermal Synthesis of Polyimide-Based Covalent Organic Frameworks.

Despite its abundance, water is not widely used as a medium for organic reactions. However, under geothermal conditions, water exhibits unique physicochemical properties, such as viscosity and a dielectric constant, and the ionic product become similar to those of common organic solvents. We have synthesized highly crystalline polyimide-based covalent organic frameworks (PICs) under geomimetic hydrothermal conditions. By exploiting triphenylene-2,3,6,7,10,11-hexacarboxylic acid in combination with various aromatic diamines, PICs with various pore dimensions and crystallinities were synthesized. XRD, FT-IR, and DFT calculations revealed that the solubility of the oligomeric intermediates under hydrothermal conditions affected the stacking structures of the crystalline PICs. Furthermore, the synthesized PICs demonstrate promising potential as an anode material in lithium-ion batteries owing to its unique redox-active properties and high surface area.