Granular materials, composed of densely packed particles, are known to possess unique mechanical properties that are highly dependent on the surface structure of the particles. A microscopic understanding of the structure‐property relationship in these systems remains unclear. Here, supra‐nanoparticle clusters (SNPCs) with precise structures are developed as model systems to elucidate the unexpected elastic behaviors. SNPCs are prepared by coordination‐driven assembly of polyhedral oligomeric silsesquioxane (POSS) with metal‐organic polyhedron (MOP). Due to the disparity in sizes, the POSS‐MOP assemblies, like their classic nanoparticles counterparts, ordering is suppressed, and the POSS‐MOP mixtures will vitrify or jam as a function of decreasing temperature. An unexpected elasticity is observed for the SNPC assemblies with a high modulus that is maintained at temperatures far beyond the glass transition temperature. From studies on the dynamics of the hierarchical structures of SNPCs and molecular dynamic simulation, the elasticity has its origins in the interpenetration of POSS‐ended arms. The physical molecular interpenetration and inter‐locking phenomenon favors the convenient solution or pressing processing of the novel cluster‐based elastomers.

Films that can maintain their flexibilities and conductivities under low humidity and broad temperature range represent the next generation of solid-state proton conductors, which would extend the applications of energy storage and conversion devices in extreme environments. Owing to their strong interactions with poly­(ethylene oxide) (PEO), polyoxometalates (POMs), a group of nanoscale metal oxide clusters, can form stable nanocomposites with PEO and fully inhibit its crystallization, facilitating the fast dynamics of PEO chains/segments, as evidenced from dielectric spectroscopy studies. It thus enables the fast proton transportation in the PEO matrix and the improvement of the composites’ proton conductivities. With POMs’ loading ratio approaching to 70% wt, the nanocomposite’s proton conductivity reaches as high as 6.86 × 10–3 S cm–1 at 100 °C in anhydrous environment. The composites’ mechanical properties can be further optimized upon the tuning of PEOs’ molecular weight and finally, a flexible, self-supported anhydrous proton conductor can be obtained, which also demonstrates high compatibility to electrodes. The nanocomposite can maintain promising proton conductivities ranging from −20 to 100 °C in an anhydrous environment, enabling the fabrication of long-term robust performance of supercapacitor devices under extreme conditions, which has never been achieved before.

The network structure in the amorphous domain of swollen iodine-doped poly (vinyl alcohol) (PVA) were systematically investigated by low-field (LF) NMR techniques to reveal the PVA-iodine complex formation mechanism. Three...

Metal-organic polyhedra (MOPs) possess micro-porous framework and impose hierarchical constraints on their surface ligands, leading to the long-ignored, logarithmic ligand exchange dynamics. Herein, the polymer networks with MOP as nanoscale crosslinkers (MOP-CNs) can integrate its unique ligand exchange dynamics and micro-porosity, affording the vitrimerlike gas separation membranes with promising mechanical performance and (re)processability. All the ligands on MOP surface are confined and correlated via the 3D coordination framework and their space neighboring, giving rise to high energy barrier for ligand exchange. Therefore, MOP-CNs demonstrate high mechanical strengths at room temperature due to their negligible ligand dynamics. The thermo-activated ligand exchange process with integrated network topology enables facile (re)processing and high solveresistance at high temperatures. This finally facilitates Arrhenius type temperature dependence of flowability and stress relaxation, giving rise to the simultaneous achievement of promising mechanical strengths and (re)processability. Finally, the cage topologies of MOPs endow the materials with bonusing micro-porous feature, and spur their applications as gas separation membranes.

Granular materials, composed of densely packed particles, are known to possess unique mechanical properties that are highly dependent on the surface structure of the particles. A microscopic understanding of the structure‐property relationship in these systems remains unclear. Here, supra‐nanoparticle clusters (SNPCs) with precise structures are developed as model systems to elucidate the unexpected elastic behaviors. SNPCs are prepared by coordination‐driven assembly of polyhedral oligomeric silsesquioxane (POSS) with metal‐organic polyhedron (MOP). Due to the disparity in sizes, the POSS‐MOP assemblies, like their classic nanoparticles counterparts, ordering is suppressed, and the POSS‐MOP mixtures will vitrify or jam as a function of decreasing temperature. An unexpected elasticity is observed for the SNPC assemblies with a high modulus that is maintained at temperatures far beyond the glass transition temperature. From studies on the dynamics of the hierarchical structures of SNPCs and molecular dynamic simulation, the elasticity has its origins in the interpenetration of POSS‐ended arms. The physical molecular interpenetration and inter‐locking phenomenon favors the convenient solution or pressing processing of the novel cluster‐based elastomers.