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Developing versatile ionoelastomers, the alternatives to hydrogels and ionogels, will boost the advancement of high-performance ionotronic devices. However, meeting the requirements of bio-derivation, high toughness, high stretchability, autonomous self-healing ability, high ionic conductivity, reprocessing, and favorable recyclability in a single ionoelastomer remains a challenging endeavor. Herein, a dynamic covalent and supramolecular design, lipoic acid (LA)-based dynamic covalent ionoelastomer (DCIE), is proposed via melt building covalent adaptive networks with hierarchically dynamic bonding (CAN-HDB), wherein lithium bonds aid in the dissociation of ions and the integration of dynamic disulfide metathesis, lithium bonds, and binary hydrogen bonds enhances the mechanical performances, self-healing capability, reprocessing, and recyclability. Therefore, the trade-off among mechanical versatility, ionic conductivity, self-healing capability, reprocessing, and recyclability is successfully handled. The obtained DCIE demonstrates remarkable stretchability (1011.7%), high toughness (3877 kJ m-3), high ionic conductivity (3.94 × 10-4 S m-1), outstanding self-healing capability, reprocessing for 3D printing, and desirable recyclability. Significantly, the selective ion transport endows the DCIE with multisensory feature capable of generating continuous electrical signals for high-quality sensations towards temperature, humidity, and strain. Coupled with the straightforward methodology, abundant availability of LA and HPC, as well as multifunction, the DCIEs present new concept of advanced ionic conductors for developing soft ionotronics.

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One-dimensional nanomaterials have become one of the most available nanoreinforcing agents for developing next-generation high-performance functional self-healing composites owing to their unique structural characteristics and surface electron structure. However, nanoscale control, structural regulation, and crystal growth are still enormous challenges in the synthesis of specific one-dimensional nanomaterials. Here, oxygen-defective MoO3-x nanowires with abundant surface dynamic bonding were successfully synthesized as novel nanofillers and photothermal response agents combined with a polyurethane matrix to construct composite elastomers, thus achieving mechanically enhanced and self-healing properties. Benefiting from the surface plasmon resonance of the MoO3-x nanowires and interfacial multiple dynamic bonding interactions, the composite elastomers demonstrated strong mechanical performance (with a strength of 31.45 MPa and elongation of 1167.73%) and ultrafast photothermal toughness self-healing performance (20 s and an efficiency of 94.34%). The introduction of MoO3-x nanowires allows the construction of unique three-dimensional cross-linked nanonetworks that can move and regulate interfacial dynamic interactions under 808 nm infrared laser stimulation, resulting in controlled mechanical and healing performance. Therefore, such special elastomers with strong photothermal responses and mechanical properties are expected to be useful in next-generation biological antibacterial materials, wearable devices, and artificial muscles.

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Metallo-supramolecular polymer networks (MSPNs) are fabricated from the crosslinking of polymers by discrete supramolecular coordination complexes. Due to the availability of various coordination complexes, e. g., 2D macrocycles and 3D nanocages, the MSPNs have been recently developed with broadly tunable visco-elasticity and enriched functions inherited from the coordination complexes. The coordination complexes possess enriched topologies and unique structural relaxation dynamics, rendering them the capability to break the traditional tradeoffs of polymer systems for the design of materials with enhanced mechanical performance. The structure-property relationship studies are critical for the material-by-design of MSPNs, while the spatiotemporal investigations are desired for the exploration of dynamics information. The work summarizes recent studies on the unique ligand-exchange kinetics and the multi-level structural relaxation dynamics of MSPNs. The MSPNs' mechanical properties can be quantitatively correlated with the dynamics for understanding the structure-property relationship. This concept will not only serve to attract more researchers to engage in the study of the structure-activity relationship of MSPNs but also inspire innovative research findings pertaining to the application of MSPNs.

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In recent decades, polymer semiconductors, extensively employed as charge transport layers in devices like organic field-effect transistors (OFETs), have undergone thorough investigation due to their capacity for large-area solution processing, making them promising for mass production. Research efforts have been twofold: enhancing the charge mobilities of polymer semiconductors and augmenting their mechanical properties to meet the demands of flexible devices. Significant progress has been made in both realms, propelling the practical application of polymer semiconductors in flexible electronics. However, integrating excellent semiconducting and mechanical properties into a single polymer still remains a significant challenge. This review intends to introduce the design strategies and discuss the properties of high-charge mobility stretchable conjugated polymers. In addition, another key challenge faced in this cutting-edge field is maintaining stable semiconducting performance during long-term mechanical deformations. Therefore, this review also discusses the development of healable polymer semiconductors as a promising avenue to improve the lifetime of stretchable device. In conclusion, challenges and outline future research perspectives in this interdisciplinary field are highlighted.

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Most plastics originate from limited petroleum reserves and cannot be effectively recycled at the end of their life cycle, making them a significant threat to the environment and human health. Closed-loop chemical recycling, by depolymerizing plastics into monomers that can be repolymerized, offers a promising solution for recycling otherwise wasted plastics. However, most current chemically recyclable polymers may only be prepared at the gram scale, and their depolymerization typically requires harsh conditions and high energy consumption. Herein, it reports less petroleum-dependent closed-loop recyclable silica-based nanocomposites that can be prepared on a large scale and have a fully reversible polymerization/depolymerization capability at room temperature, based on catalysis of free aminopropyl groups with the assistance of diethylamine or ethylenediamine. The nanocomposites show glass-like hardness yet plastic-like light weight and toughness, exhibiting the highest specific mechanical strength superior even to common materials such as poly(methyl methacrylate), glass, and ZrO2 ceramic, as well as demonstrating multifunctionality such as anti-fouling, low thermal conductivity, and flame retardancy. Meanwhile, these nanocomposites can be easily processed by various plastic-like scalable manufacturing methods, such as compression molding and 3D printing. These nanocomposites are expected to provide an alternative to petroleum-based plastics and contribute to a closed-loop materials economy.

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Conventional semiconductor nanocrystals exhibit wide-ranging optical behavior, whereas the size-dependent photophysical properties of metal-organic framework (MOF) nanocrystals remain an open research frontier. Here, we present size- and temperature-dependent optical absorption spectra of common MOFs with particle sizes ranging from tens of nanometers to several micrometers. All materials exhibit optical gaps that decrease at elevated temperatures, which we attribute to the dynamic nature of MOF metal-linker bonds. Accordingly, whereas the labile titanium-carboxylate bonds of MIL-125 give rise to bandgaps that red-shift by ∼600 meV over 300 K, the more rigid zinc-imidazolate bonds of ZIF-8 produce a red-shift of only ∼10 meV. Furthermore, smaller particles induce far larger decreases to optical gaps. Taken together, these results suggest MOF bonding becomes more flexible with smaller nanocrystal sizes, offering a powerful tool for manipulating optical behavior through composition, temperature, and dimensionality.

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Metal-organic frameworks have developed into a formidable heterogeneous catalysis platform in recent years. It is well established that thermolysis of coordinated solvents from MOF nodes can render highly reactive, coordinatively unsaturated metal complexes which are stabilized via site isolation and serve as active sites in catalysis. Such approaches are limited to frameworks featuring solvated transition-metal complexes and must be stable toward the formation of "permanent" open metal sites. Herein, we exploit the hemilability of metal-carboxylate bonds to generate transient open metal sites in an In(III) MOF, pertinent to In-centered catalysis. The transient open metal sites catalyze the Strecker reaction over multiple cycles without loss of activity or crystallinity. We employ computational and spectroscopic methods to confirm the formation of open metal sites via transient dissociation of In(III)-carboxylate bonds. Furthermore, the amount of transient open metal sites within the material and thus the catalytic performance can be temperature-modulated.

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Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network-structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advantages in terms of gel stability, reversibility, or tunability and presents new opportunities for the design of reconfigurable materials and fueled assemblies.

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Covalent adaptable networks (CANs) based on the thiol-Michael (TM) linkages can be thermal and pH responsive. Here, a new vinyl-sulfone-based thiol-Michael crosslinker is synthesized and incorporated into acrylate-based CANs to achieve stable materials with dynamic properties. Because of the reversible TM linkages, excellent temperature-responsive re-healing and malleability properties are achieved. In addition, for the first time, a photoresponsive coumarin moiety is incorporated with TM-based CANs to introduce light-mediated reconfigureability and postpolymerization crosslinking. Overall, these materials can be on demand dynamic in response to heat and light but can retain mechanical stability at ambient condition.

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Inspired by protein polymerizations, much progress has been made in making "polymer-like" supramolecular structures from small synthetic subunits through non-covalent bonds. A few regulation mechanisms have also been explored in synthetic platforms to create supramolecular polymers and materials with dynamic properties. Herein, a type of reactive regulator that facilitates the dimerization of the monomer precursors through dynamic bonds to trigger the supramolecular assembly from small molecules in an aqueous solution is described. The supramolecular structures are crystalline in nature and the reaction coupled assembly strategy can be extended to a supramolecular assembly of aromatic amide derivatives formed in-situ. The method may be instructive for the development of supramolecular nanocrystalline materials with desired physical properties.

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A new approach for reprocessing of existing thermoset waste is presented. This work demonstrates that unrecyclable thermoset materials can be reprocessed using the concept of associative dynamic bonding, vitrimers. The developed recycling methodology relies on swelling the thermoset network into a solution of a catalyst, which enables transesterification reactions allowing dynamic bond exchange between ester and hydroxyl groups within the thermoset network. Thermal and mechanical properties for recycled polyurethane and epoxy networks are studied and a strategy to maintain the properties of recycled materials is discussed. The developed methodology promises recycling and even upcycling and reprocessing of previously thought intractable materials. Moreover, processability of vitrimerized thermosets with common thermoplastic manufacturing methods opens up the possibility of tuning recycled networks by adding nanoparticles. This flexibility keeps the application window of recycled thermosets very broad.

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Marine mussels use catechol-rich interfacial mussel foot proteins (mfps) as primers that attach to mineral surfaces via hydrogen, metal coordination, electrostatic, ionic, or hydrophobic bonds, creating a secondary surface that promotes bonding to the bulk mfps. Inspired by this biological adhesive primer, it is shown that a ≈1 nm thick catecholic single-molecule priming layer increases the adhesion strength of crosslinked polymethacrylate resin on mineral surfaces by up to an order of magnitude when compared with conventional primers such as noncatecholic silane- and phosphate-based grafts. Molecular dynamics simulations confirm that catechol groups anchor to a variety of mineral surfaces and shed light on the binding mode of each molecule. Here, a ≈50% toughness enhancement is achieved in a stiff load-bearing polymer network, demonstrating the utility of mussel-inspired bonding for processing a wide range of polymeric interfaces, including structural, load-bearing materials.

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Dynamic bonding materials are of high interest in a variety of fields in material science. The reversible nature of certain reaction classes is frequently employed for introducing key material properties such as the capability to self-heal. In addition to the synthetic effort required for designing such materials, their analysis is a highly complex--yet important--endeavor. Herein, we critically review the current state of the art analytical methods and their application in the context of reversible bonding on demand soft matter material characterization for an in-depth performance assessment. The main analytical focus lies on the characterization at the molecular level.

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