Cation-π and electrostatic interactions co-driven assembly of two-dimensional heteropore supramolecular polymers with rapid iodine capture capability

Constructing two-dimensional (2D) supramolecular polymers with complicated hierarchical porosity significantly contributes to developing effective strategies to control delicate self-assembly architectures, thus facilitating the fabrication of advanced 2D organic functional materials. Here, we report utilizing cooperative cation-π and electrostatic interactions to construct a series of robust 2D heteropore supramolecular polymers (2D HPSPs) with hierarchical pore structures, in which hexagonal and rectangular pores are alternately and periodically arranged, and the pore sizes can be finely tuned. Remarkably, the as-prepared 2D HPSPs exhibit excellent iodine (I₂) capture rate (a maximum K _80% value is 2.25 g h⁻¹), and present a novel mechanism involving transport-adsorption spatiotemporal separation for rapid I₂ capture. In this mechanism, the transport of free I₂ is first conducted in large hexagonal pores, and then I₂ can be preferentially adsorbed in small rectangular pores, thereby preventing the transfer channels from blocking and greatly improving the adsorption kinetics. [Figure not available: see fulltext.]