Solvent-Free Synthesis of C=N Linked Two-Dimensional Covalent Organic Frameworks.

Covalent organic frameworks (COFs) are an emerging class of porous crystalline polymers with well-defined structures and tunable functionalities, which have fascinating applications in a wide range of fields. However, the synthetic procedures of COFs are mainly confined to the solvothermal synthesis method which usually requires harsh experimental conditions. In this work, an effective solvent-free synthesis method to construct a series of two-dimensional (2D) COFs including imine-linked, azine-linked, ß-ketoenamine-linked, which avoids the complicated solvent screening process and most of the disadvantages of solvothermal methods is developed. The crystallinity and porosity of these COFs are comparable to those prepared by traditional solvothermal routes. What's more, the advantages of the solvent-free method enable the production of gram-scale of those 2D COFs through a one-pot reaction, demonstrating high industrial application potentials.

Engineering Covalent Organic Frameworks with Polyethylene Glycol as Self-Sustained Humidity-Responsive Actuators.

Regarding the global energy crisis, it is of profound significance to develop spontaneous power generators that harvest natural energy. Fabricating humidity-responsive actuators that can conduct such energy transduction is of paramount importance. Herein, we incorporate covalent organic frameworks with flexible polyethylene glycol to fabricate rigid-flexible coupled membrane actuators. This strategy significantly improves the mechanical properties and humidity-responsive performance of the actuators, meanwhile, the existence of ordered structures enables us to unveil the actuation mechanism. These high-performance actuators can achieve various actuation applications and exhibit interesting self-oscillation behavior above a water surface. Finally, after being coupled with a piezoelectric film, the bilayer device can spontaneously output electricity over 2 days. This work paves a new avenue to fabricate rigid-flexible coupled actuators for self-sustained energy transduction.

Rational Construction of Borromean Linked Crystalline Organic Polymers.

Attributed to the unique topological complexity and elegant beauty, Borromean systems are attracting intense attention. However, at present, the construction of Borromean linked organic polymers remains a challenge. To address this formidable challenge, we developed a supramolecular-synthon-driven approach to fabricate Borromean linked organic polymer. The solvothermal condensation reaction of a judiciously selected trigonal pyramidal building block, 1,3,5-Tris(4-aminophenyl)adamantane, with linear dialdehyde building blocks allowed the construction of two rare covalent organic frameworks (COFs) with high crystallinity and robustness. Structure refinement unveiled the successful formation of entangled 2D→2D Borromean arrayed structures. Both the two COFs were of microporosity and thus demonstrated the potentials for gas separation. The successful synthesis of the first two Borromean linked organic polymers paves the avenue to expand the supramolecular-synthon-driven approach to other building blocks and topologies, and broadens the family and scope of COFs.

Fabrication of Photoresponsive Crystalline Artificial Muscles Based on PEGylated Covalent Organic Framework Membranes.

Seeking new photoresponsive materials with high energy conversion efficiency, good mechanical properties, as well as well-defined photoactuation mechanisms is of paramount significance. To address these challenges, we first introduced crystalline covalent organic frameworks (COFs) into the photoactuator field and created a facile fabrication strategy to directly install photoresponsive functional groups (i.e., acylhydrazone) on the skeletons of COFs. Herein, an approach to use polyethylene glycol (PEG) cross-linked dimers as the building blocks of the COF-42 platform was developed and afforded a series of uniform and freestanding membranes (PEG-COF-42) with outstanding mechanical properties (e.g., high flexibility and mechanical strength). Notably, these membranes possessed a fast mechanical response (e.g., bending) to UV light and good reversibility upon blue light or heating. After an in-depth investigation of the photoactuation mechanism via various techniques, we proposed a mechanism for the photoresponsive performance of PEG-COF-42: configurational change of acylhydrazone (i.e., E ↔ Z isomerization) accompanied by an excited-state intramolecular proton transfer (ESIPT) process intramolecularly transferring hydrogens from hydrogen donors (N-H) to hydrogen acceptors (oxygen in PEG). Moreover, attributed to the PEG moieties, PEG-COF-42 also demonstrated a vapor-responsive performance. This study not only broadens the application scopes of COFs but also provides new opportunities for the construction of multi-stimuli-responsive materials.