Controllable construction of an ordered three-dimensional supramolecular polymer with selective guest adsorption ability

Three-dimensional supramolecular polymers (3DSPs) have received considerable attention in recent years due to the use of dynamically reversible non-covalent interactions, which can endow 3DSPs with attractive functions. However, the resulting 3DSPs typically exhibit fragile mechanical robustness and poor periodicity in 3D space because the dissociation energy of representative non-covalent bonds is lower than that of the covalent bond generally. Herein, we propose a cation-π-based “sandwich”-like binding pattern between two monomers, for the preparation of an ordered and stable 3DSP having 4-fold interpenetrated nets (dia-3DSP). We also revealed that the binding driving force and stoichiometric ratio of monomer pairs have a strong impact on the dynamic process of 3D self-assembly. The as-prepared dia-3DSP can selectively adsorb molecules of similar sizes in accordance with the molecular charge. Our results provide a proof-of-concept for a new strategy to control the molecular 3D self-assembly process and pave a new way to prepare ordered, stable, and functional supramolecular materials.