PolyCOFs: A New Class of Freestanding Responsive Covalent Organic Framework Membranes with High Mechanical Performance

[Image: see text] Traditional covalent organic frameworks (COFs) are prepared via polymerization based on small molecular monomers. However, the employment of polymers as building blocks to construct COFs has not been reported yet. Herein, we create a new concept of polymer covalent organic frameworks (polyCOFs) formed by linear polymers as structural building blocks, which inherit the merits from both COFs and linear polymers. PolyCOFs represent a new category of porous COF materials that demonstrate good crystallinity and high stability. More importantly, benefiting from the flexibility and processability of a linear polymer, polyCOFs can spontaneously form defect-free, flexible, and freestanding membranes that exhibit excellent mechanical properties and undergo reversible mechanical transformation upon exposure to various organic vapors. For the first time, we demonstrated that polyCOF membranes can be used as artificial muscles to perform various complicated motions (e.g., lifting objects, doing “sit-ups”) triggered by vapors. This study bridges the gap between one-dimensional amorphous linear polymers and crystalline polymer frameworks and paves a new avenue to prepare stimuli-responsive actuators using porous COF materials.