Insights into the Correlation of Microscopic Motions of [c2]Daisy Chains with Macroscopic Mechanical Performance for Mechanically Interlocked Networks.

Mimicking filament sliding in sarcomeres using artificial molecular muscles such as [c2]daisy chains has aroused increasing interest in developing advanced polymeric materials. Although few bistable [c2]daisy chain-based mechanically interlocked polymers (MIPs) with stimuli-responsive behaviors have been constructed, it remains a significant challenge to establish the relationship between microscopic responsiveness of [c2]daisy chains and macroscopic mechanical properties of the corresponding MIPs. Herein, we report two mechanically interlocked networks (MINs) consisting of dense [c2]daisy chains with individual extension (MIN-1) or contraction (MIN-2) conformations decoupled from a bistable precursor, which serve as model systems to address the challenge. Upon external force, the extended [c2]daisy chains in MIN-1 mainly undergo elastic deformation, which is able to assure the strength, elasticity, and creep resistance of the corresponding material. For the contracted [c2]daisy chains, long-range sliding motion occurs along with the release of latent alkyl chains between the two DB24C8 wheels, and accumulating lots of such microscopic motions endows MIN-2 with enhanced ductility and ability of energy dissipation. Therefore, by decoupling a bistable [c2]daisy chain into individual extended and contracted ones, we directly correlate the microscopic motion of [c2]daisy chains with macroscopic mechanical properties of MINs.

Robust and Dynamic Polymer Networks Enabled by Woven Crosslinks.

Crosslinking plays a crucial role in determining mechanical properties of polymer materials. Although various crosslinks based on covalent or noncovalent bonds have been adopted, it remains an enormous challenge to develop a crosslink which could endow corresponding polymer network with robust yet dynamic properties. Herein, we report a crosslink simultaneously having dynamic property and woven geometry, and the polymer network with woven crosslinks (WPN) could integrate the merits of covalent polymer network (CPN) and supramolecular polymer network (SPN). In specific, the WPN not only exhibits comparable stiffness, strength, elastic recovery, and anti-fatigue property to those of CPN, but also possesses decent mechanical adaptivity and ductility, similar to those of SPN. Particularly, its toughness and puncture resistance are much superior to those of the others. Besides, the dynamicity of woven crosslink also imparts good performances of self-healing and processability to WPN.

Drum-like Metallacages with Size-Dependent Fluorescence: Exploring the Photophysics of Tetraphenylethylene under Locked Conformations.

Materials with aggregation-induced emission (AIE) properties are of growing interest due to their widespread applications. AIEgens, such as tetraphenylethylene units, display varying emission behaviors during their conformational changes. However, the structure-property relationships of the intermediate conformations have rarely been explored. Herein, we show that the conformational restriction on TPE units can affect the structural relaxation in the excited state and the resulting photophysical behaviors. Specifically, three metallacages of different sizes were prepared via the coordination-driven self-assembly of a TPE-based tetrapyridyl donor with length-increasing Pt(II) acceptors. While the metallacages share similar scaffolds, they exhibit a trend of red-shifted fluorescence and attenuated quantum yield with the increase of their sizes. Furthermore, spectroscopic and computational studies together with a control experiment were conducted, revealing that the degree of cage tension imposed on the excited-state conformational relaxation of TPE moieties resulted in their distinct photophysical properties. The precise control of conformation holds promise as a strategy for understanding the AIE mechanism as well as optimizing the photophysical behaviors of materials on the platform of supramolecular coordination complexes.

Woven Polymer Networks via the Topological Transformation of a [2]Catenane.

Weaving technology has been widely used to manufacture macroscopic fabrics to meet the artistic and practical needs of humanity for thousands of years. However, the fabrication of molecular fabrics with fascinating topologies and unique mechanical properties represents a significant challenge. Herein, we describe a topological transformation strategy to construct woven polymer networks (WPNs) at the molecular level via ring-opening metathesis polymerization (ROMP) of a zinc-template [2]catenane. The key feature of this approach is the exploitation of the pre-existing catenane crossing points that maintain the dense woven structure and the flexible alkyl chains on the [2]catenane that synergistically work with the crossing points to modulate the physicochemical and mechanical properties of the woven materials. As a result, the WPN possesses a certain degree of flexibility and stretchability, as well as high thermostability and mechanical robustness. Furthermore, we could remove the zinc ions to endow the WPN with more degrees of freedom and then enhance its mechanical behaviors by remetalation. This study not only provides a novel strategy toward woven materials with intriguing structural features and emergent mechanical adaptivities, but also highlights that mechanically interlocked molecules could offer unique opportunities for the construction of smart supramolecular materials with peculiar interlaced topologies at the molecular scale.

Trackable Supramolecular Fusion: Cage to Cage Transformation of Tetraphenylethylene-Based Metalloassemblies.

Herein, the trackable supramolecular transformation of a two-component molecular cage to a three-component cage through supramolecular fusion with another two-component molecular square is described. The use of tetraphenylethene (TPE), a chromophore with aggregation-induced emission (AIE) character, as a component for the molecular cages enables facile fluorescence monitoring of the transformation process: while both cages exhibit fluorescence emission via the restriction of intramolecular motion of the TPE motif, the interactions between TPE and 4,4'-bipyridine introduced in the supramolecular fusion process result in partial fluorescence quenching and shifts in the emission maximum. This study provides a simple and efficient approach towards complex supramolecular cages with emergent functions and demonstrates that AIE features could provide unique opportunities for the characterization of complex, dynamic supramolecular transformation processes.

Synergistic Covalent-and-Supramolecular Polymers with an Interwoven Topology.

Network topologies, especially some high-order topologies, are able to furnish cross-linked polymer materials with enhanced properties without altering their chemical composition. However, the fabrication of such topologically intriguing architectures at the macromolecular level and in-depth insights into their structure-property relationship remain a significant challenge. Herein, we relied on synergistic covalent-and-supramolecular polymers (CSPs) as a platform to prepare a range of polymer networks with an interwoven topology. Specifically, through the sequential supramolecular self-assemblies, the covalent polymers (CPs) and metallosupramolecular polymers (MSPs) could be interwoven in our CSPs by [2]pseudorotaxane cross-links. As a result, the obtained CSPs possessed a topological network that could not only promote the synergistic effect between CPs and MSPs to afford mechanically robust yet dynamic materials but also vest polymers with some functions, as manifested by force-induced hierarchical dissociations of supramolecular interactions and superior thermomechanical stability compared to our previously reported CSP systems. Furthermore, our CSPs exhibited tunable mechanical performance toward multiple stimuli including K+ and PPh3, demonstrating abundant stimuli-responsive properties. We hope that these findings could provide novel opportunities toward achieving topological structures at the macromolecular level and also motivate further explorations of polymeric materials via the way of controlling their topological structures.

Amplification of integrated microscopic motions of high-density [2]rotaxanes in mechanically interlocked networks.

Integrating individual microscopic motion to perform tasks in macroscopic sale is common in living organisms. However, developing artificial materials in which molecular-level motions could be amplified to behave macroscopically is still challenging. Herein, we present a class of mechanically interlocked networks (MINs) carrying densely rotaxanated backbones as a model system to understand macroscopic mechanical properties stemmed from the integration and amplification of intramolecular motion of the embedded [2]rotaxane motifs. On the one hand, the motion of mechanical bonds introduces the original dangling chains into the network, and the synergy of numerous such microscopic motions leads to an expansion of entire network, imparting good stretchability and puncture resistance to the MINs. On the other hand, the dissociation of host-guest recognition and subsequent sliding motion represent a peculiar energy dissipation pathway, whose integration and amplification result in the bulk materials with favorable toughness and damping capacity. Thereinto, we develop a continuous stress-relaxation method to elucidate the microscopic motion of [2]rotaxane units, which contributes to the understanding of the relationship between cumulative microscopic motions and amplified macroscopic mechanical performance.

Mechanically interlocked networks cross-linked by a molecular necklace.

Molecular necklaces have attracted much research attention due to their unique topological structures. Although numerous molecular necklaces with exquisite structures have been constructed, it remains a major challenge to exploit the functions and applications associated with their fascinating architectural and dynamic characteristics. Herein, we report a class of mechanically interlocked networks (MINs) cross-linked by a molecular necklace, in which multiple crown ethers are threaded on a hexagonal metallacyclic framework to furnish a cross-linker with delicate interlocked structures. The molecular necklace cross-linker possesses multiple peculiar advantages: multivalent interactions and rigid metallacycle framework guarantee robust features of MINs while the motion and dissociation of the interlocked structures bring in notable mechanical adaptivity. Moreover, the MINs could respond to the stimuli of K+ and Br-, which lead to the dethreading of crown ether and even the complete decomposition of molecular necklace, respectively, showing abundant active properties. These findings demonstrate the untapped potential of molecular necklaces as cross-linkers and open the door to extend their advanced applications in intelligent supramolecular materials.

Synergistic combination of ACQ and AIE moieties to enhance the emission of hexagonal metallacycles.

Herein, we show the synergistic combination of aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE) units into two hexagonal metallacycles. The resultant metallacycles displayed emergent photophysical properties including tunable fluorescence using the polarity and solubility of the solvents as well as enhanced emissive efficacy. Our work demonstrates the synergistic enhancement of these two orthogonal effects via coordination-driven self-assembly.