Monodispersed hairy nanocomposites with typical 2 nm (isophthalic acid)24Cu24 metal–organic polyhedra (MOP) as a core protected by 24 polymer chains with controlled narrow molecular weight distribution has been probed by imaging and scattering studies for the heterogeneity of polymers in the nanocomposites and the confinement effect the MOPs imposing on anchored polymers. Typical confined‐extending surrounded by one entanglement area is proposed to describe the physical states of the polymer chains. This model dictates the counterintuitive thermal and rheological properties and prohibited solvent exchange properties of the nanocomposites, whilst those polymer chain states are tunable and deterministic based on their component inputs. From the relationship between the structure and behavior of the MOP nanocomposites, a MOP‐composited thermoplastic elastomer was obtained, providing practical solutions to improve mechanical/rheological performances and processabilities of inorganic MOPs.

Materials under space confinement can alter their physical and chemical properties, paving the way for new science and novel applications. Nanoparticles can enforce spatial constraints on the polymers densely grafted on their surfaces, which can effectively change polymers’ thermal/mechanical properties and finally lead to significant mechanical reinforcement for the obtained nanocomposites. Here, we describe the confinement effect that metal–organic polyhedron (MOPs), nanoparticles with monodispersed and ultrasmall sizes (∼2 nm), impose to the 24 poly­(N-isopropylacrylamide) (PNiPAM) chains grafted on their surface. The curved surface of the MOP brings unique confinement to the grafted PNiPAMs: the inner fraction of PNiPAM chains is under ultraconfinement, while the outer fraction is almost free. Suggested from small angle neutron scattering studies, the outer layer polymers stay hydrated and help solvate the nanocomposites in water, while the inner polymer layer prohibits the water penetration into MOP area and contributes to the high stability of the MOPs. Such a confinement effect further influences the thermoresponsiveness of PNiPAM–MOPs in solutions and enhances their efficiency for controlled separation and release of small molecules.

Despite the fact that numerous studies have been conducted to explore the crystalline structures of various metal−organic polyhedrons (MOPs), the direct probing of solvated and deformed structures of MOPs is still rare but critical to the development of processing protocols and the understanding of their structure−property relationship for gas separation and ion transportation. Here, MOPs from the coordination of isophthalic acids and Cu 2+ are covalently functionalized with alkyl chains for studies in solutions and at the air/water interface, respectively. As suggested from small-angle scattering studies, the MOP structures in the solvated state remain intact while the grafted linear alkyl arms exhibit an extended conformation, allowing solvent molecules to penetrate into the cavity of MOPs. Meanwhile, under surface pressure at the water/air interface, the hairy MOP structures, as suggested by in situ neutron reflectivity studies, can be deformed and MOP cores are close together while the grafted chains are squeezed upward and downward toward liquid and air phases, respectively. This discovery provides the first direct evidence for the existence of an ion transportation active conformation of hairy MOPs.

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.

With access to the solution structures of nanocomposites of coordination nanocages (CNCs) via scattering and chromatography techniques, their mysterious solution dynamics have been, for the first time, resolved, and interestingly, the surface macromolecules can be substituted by extra free macromolecules in solutions. Obvious exchange of macromolecules can be observed in the solution mixtures of CNC nanocomposites at high temperatures, revising the understanding of the dynamics of CNC nanocomposites. Being distinct from nanocomposites of a simple coordination complex, the quantified solution dynamics of CNC nanocomposites indicates a typical logarithmic time dependence with the dissociation of surface macromolecules as the thermodynamically limiting step, suggesting strongly coupled and hierarchically constrained dynamics among the surface macromolecules. Their dynamics can be activated only upon application of high temperature or selected solvents, and therefore, the rational design of polymer assemblies, for example, hybrid-arm star polymers with precisely controlled compositions and reprocessable, robust CNC-cross-linked supramolecular polymer networks, is facilitated.