Three‐Dimensional Anionic Cyclodextrin‐Based Covalent Organic Frameworks

Three‐dimensional covalent organic frameworks (3D COFs) are promising crystalline materials with well‐defined structures, high porosity, and low density; however, the limited choice of building blocks and synthetic difficulties have hampered their development. Herein, we used a flexible and aliphatic macrocycle, namely γ‐cyclodextrin (γ‐CD), as the soft struts for the construction of a polymeric and periodic 3D extended network, with the units joined via tetrakis(spiroborate) tetrahedra with various counterions. The inclusion of pliable moieties in the robust open framework endows these CD‐COFs with dynamic features, leading to a prominent Li ion conductivity of up to 2.7 mS cm⁻¹ at 30 °C and excellent long‐term Li ion stripping/plating stability. Exchanging the counterions within the pores can effectively modulate the interactions between the CD‐COF and CO₂ molecules.