Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis

[Image: see text] Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous catalysts. Herein, we report the synthesis and characterization of a series of novel microporous Tröger’s base polymers and copolymers (TB-PIMs) with tunable pore size. The basicity of TB sites is exploited to catalyze the Knoevenagel condensation of benzaldehydes and malononitrile, and the dimension of the pores can be systematically adjusted with an appropriate selection of monomers and comonomers. The tunability of the pore size provides the enhanced accessibility of the catalytic sites for substrates, which leads to a great improvement in conversions, with the best results achieving completion in only 20 min. In addition, it enables the use of large benzaldehydes, which is prevented when using polymers with very small pores, typical of conventional PIMs. The catalytic reaction is more efficient than the corresponding homogeneous counterpart and is ultimately optimized with the addition of a small amount of a solvent, which facilitates the swelling of the pores and leads to a further improvement in the performance and to a better carbon economy. Molecular dynamic modeling of the copolymers’ structures is employed to describe the swellability of flexible chains, helping the understanding of the improved performance and demonstrating the great potential of these novel materials.