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Abstract Polymer networks, which are materials composed of many smaller components—referred to as “junctions” and “strands”—connected together via covalent or non‐covalent/supramolecular interactions, are arguably the most versatile, widely studied, broadly used, and important materials known. From the first commercial polymers through the plastics revolution of the 20^thcentury to today, there are almost no aspects of modern life that are not impacted by polymer networks. Nevertheless, there are still many challenges that must be addressed to enable a complete understanding of these materials and facilitate their development for emerging applications ranging from sustainability and energy harvesting/storage to tissue engineering and additive manufacturing. Here, we provide a unifying overview of the fundamentals of polymer network synthesis, structure, and properties, tying together recent trends in the field that are not always associated with classical polymer networks, such as the advent of crystalline “framework” materials. We also highlight recent advances in using molecular design and control of topology to showcase how a deep understanding of structure–property relationships can lead to advanced networks with exceptional properties. 

Abstract Metal–organic framework nanoparticles (MOF NPs) have emerged as an important class of materials that display significantly enhanced performance in many applications compared to bulk MOF materials; their synthesis, however, commonly involves a tedious sequence that controls particle size and surface properties in separate steps. Now, a simple strategy to access functional MOF NPs in one pot is reported that uses a polyMOF ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF‐5 NPs with sizes down to 20 nm, displaying exceptional structural and colloidal stability upon exposure to ambient conditions. A detailed time‐dependent study revealed that the polyMOF NPs were formed following an aggregation‐confined crystallization mechanism. Generality was demonstrated through the synthesis of well‐defined polyUiO‐66 NPs. 

Abstract Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre‐irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu₂₄L₂₄metal–organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this “polyMOC” material can be reversibly switched between Cu^II, Cu^I, and Cu⁰. The instability of the MOC junctions in the Cu^Iand Cu⁰states leads to network disassembly, forming Cu^I/Cu⁰solutions, respectively, that are stable until re‐oxidation to Cu^IIand supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper‐catalyzed azide‐alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks. 

Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition—elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior.