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Covalent organic frameworks (COFs) have emerged as versatile materials with many applications, such as carbon capture, molecular separation, catalysis, and energy storage. Traditionally, flexible building blocks have been avoided due to their potential to disrupt ordered structures. Recent studies have demonstrated the intriguing properties and enhanced structural diversity achievable with flexible components by judicious selection of building blocks. This study presents a novel series of ionic COFs (ICOFs) consisting of tetraborate nodes and flexible linkers. These ICOFs use borohydrides to irreversibly deprotonate the alcohol monomers to achieve a high degree of polymerization. Structural analysis confirms the dia topologies. Reticulation is explored using various monomers and metal counterions. Also, these frameworks exhibit excellent stability in alcohols and coordinating solvents. The materials have been tested as single‐ion conductive solid‐state electrolytes. ICOF‐203‐Li displays one of the lowest activation energies reported for ion conduction. This tetraborate chemistry is anticipated to facilitate further structural diversity and functionality in crystalline polymers. [ABSTRACT FROM AUTHOR]

Host‐guest chemistry, a pivotal branch of supramolecular chemistry, plays an essential role in understanding and constructing complex structures through non‐covalent interactions. Organic molecular cages, characterized by their intrinsic confined cavities, can selectively bind a variety of guest molecules. Their host–guest chemistry has been well studied in the solution phase, and several attempts have been made to encode well‐defined molecular architectures into solid‐state polymeric materials. However, only limited studies have explored their potential in the solid state, where their lack of robustness and less ordered networks significantly hinder practical applications. Herein, we report the synthesis of a single‐crystal cage framework and a systematic study of its host–guest chemistry, spanning from the solution state to the solid state. Our studies reveal that the host–guest interactions inherent to the cage are successfully maintained in the solid‐state polymeric material. Furthermore, the framework's robustness allows for the guest molecules (fullerene) to be released triggered by an organic acid (trifluoroacetic acid), with subsequent regeneration of the framework through an organic base (triethylamine) treatment. Our findings represent the first synthesis of a robust, single‐crystal cage framework exhibiting highly selective and reversible host–guest chemistry, thus showing great potential towards molecular separation application. [ABSTRACT FROM AUTHOR]

Covalent network polymers, as materials composed of atoms interconnected by covalent bonds in a continuous network, are known for their thermal and chemical stability. Over the past two decades, these materials have undergone significant transformations, gaining properties such as malleability, environmental responsiveness, recyclability, crystallinity, and customizable porosity, enabled by the development and integration of dynamic covalent chemistry (DCvC). In this review, we explore the innovative realm of covalent network polymers by focusing on the recent advances achieved through the application of DCvC. We start by examining the history and fundamental principles of DCvC, detailing its inception and core concepts and noting its key role in reversible covalent bond formation. Then the reprocessability of covalent network polymers enabled by DCvC is thoroughly discussed, starting from the significant milestones that marked the evolution of these polymers and progressing to their current trends and applications. The influence of DCvC on the crystallinity of covalent network polymers is then reviewed, covering their bond diversity, synthesis techniques, and functionalities. In the concluding section, we address the current challenges faced in the field of covalent network polymers and speculates on potential future directions. [ABSTRACT FROM AUTHOR]

Thermosets are well known for their advantages such as high stability and chemical resistance. However, developing sustainable thermosets with degradability and recyclability faces several principal challenges, including reconciling the desired characteristics during service with the recycling and reprocessing properties required at the end of life, establishing efficient methods for large-scale synthesis, and aligning with current manufacturing process. Here a general strategy is presented for the on-demand degradation and recycling of thermosets under mild conditions utilizing dynamic precursors with dual-factor-controlled reversibility. Specifically, dynamic triazine crosslinkers are introduced through dynamic nucleophilic aromatic substitution (S N Ar) into the precursor polyols used in polyurethane (PU) synthesis. Upon removal of the catalyst and alcohol, the reversibility of S N Ar is deactivated, allowing for the use of standard PU polymerization techniques such as injection molding, casting, and foaming. The resulting cyanurate-crosslinked PUs maintain high stability and diverse mechanical properties of traditional crosslinked PUs, yet offer the advantage of easy on-demand depolymerization for recycling by activating the reversibility of S N Ar under specific but mild conditions-a combination of base, alcohol, and mild heat. It is envisioned that this approach, involving the pre-installation of dual-factor-controlled dynamic crosslinkers, can be broadly applied to current thermosetting plastic manufacturing processes, introducing enhanced sustainability., (© 2024 Wiley‐VCH GmbH.)

Double-walled covalent organic frameworks, consisting of two same building blocks parallel to each other forming ladder-shape linkers, could enhance the stability of the frameworks and increase the density of functional sites, thus making them suitable for various applications. In this study, two double-walled covalent organic frameworks, namely DW-COF-1 and DW-COF-2, were successfully synthesized via imine condensation. The resulting DW-COFs exhibited a honeycomb topology, high crystallinity and stability. Particularly, DW-COF-2 showed excellent resistance toward boiling water, strong acid, and strong base, due to its double-walled structure, which limits the exposure of labile imine bonds to external chemical environments. The DW-COFs showed high porosity near 900 m 2 /g, making them suitable for gas storage/separation. The selective gas adsorption experiments showed that at 273 K and 1 atm pressure, DW-COF-1 and DW-COF-2 exhibited a good IAST selectivity towards CO 2 /N 2 (15/85) adsorption, with selectivity values of 121.3 and 56.4 for CO 2 over N 2 , respectively., (© 2023 Wiley-VCH GmbH.)