Toward Tailorable Porous Organic Polymer Networks: A High-Temperature Dynamic Polymerization Scheme Based on Aromatic Nitriles

Triazine-based polymer scaffolds with controllable porosity were prepared through a dynamic polymerization scheme based on a broad variety of aromatic nitriles, upon polytrimerization of the latter from ZnCl2 salt melts at high temperatures. In the present study, the reaction parameters such as the temperature and monomer concentration as well as the geometry and functionality of the monomers were systematically varied. A comprehensive overview of the influences of these parameters on the outcome of the polymerization reaction in terms of chemical nature and porous properties of the materials is proposed. Rather than the variation of the monomer size and/or geometry, the reaction parameters were found to play a crucial role for tuning the porosity of the materials and especially the reaction temperature. Finally, the use of functional aromatic bridging units allowed the formation of functional polymer scaffolds with the ability to coordinate metal salts, introducing the possibility to design new metallo-organic materials.