Supramolecular Polymer Frameworks with Controlled and Uniform Pore Apertures

Porous frameworks with controlled pore structure and tunable aperture are greatly demanded. However, precise synthesis of this kind of materials is a formidable challenge. Herein, we report the fabrication of two‐dimensional (2D) supramolecular polymer frameworks using a precisely synthesized rod‐like helical polyisocyanide as link. Four three‐arm star‐shaped polyisocyanides with the degree of the polymerization of 10, 20, 30 and 40, and having 2‐ureido‐4[1H]‐pyrimidinone (UPy) terminals were synthesized. 2D‐Crystalline polymer frameworks with apertures of 5.3, 10.1, 13.9, and 19.1 nm were respectively obtained through intermolecular hydrogen bonding interaction between the terminal Upy units. The pore aperture is dependent on the length of polyisocyanide backbone. Thus, well‐defined supramolecular polymer frameworks with controlled and uniform hexagonal pores were obtained, as proved by small‐angle X‐ray scattering (synchrotron radiation facility), atomic force microscopy, and Brunauer–Emmett–Teller analyses. The frameworks with uniform large pore aperture were used to purify nanomaterials and immobilize biomacromolecules. For instance, the membranes of the polymer frameworks could size‐fractionation of silver nanoparticles into uniform nanoparticles with very low dispersity. The frameworks with large aperture facilitated the inclusion of myoglobin and enhanced the stability and catalytic activity.