Photoresponsive Viscoelasticity of the Granular Materials of Azobenzene-Bearing Molecular Nanoparticles.

The large sizes of granular particles lead to their slow diffusive dynamics and significant interparticle friction, bringing enormous difficulty to tune the mechanical properties and processability of the granular materials (GMs). Herein, 1 nm polyhedral oligomeric silsesquioxane (POSS) particles functionalized with azobenzene are designed as structural units, and the obtained GMs show unique photoswitchable viscoelasticity. The azobenzene group can undergo a reversible trans-cis conformation switch while the π-π stacking among the azobenzene fragments is only favored by the trans-conformation due to molecular geometrical requirements. The POSS units from neighboring assemblies close pack to form microdomains, and the POSS is under confinement by both the supramolecular bonding and the other POSS in the microdomains. The simultaneous breaking of the two types of confinement is difficult and, therefore, the free diffusion of POSS is hindered, leading to the elasticity of the GMs of trans-POSS. For cis-POSS, the interparticle supramolecular interaction is weak and the POSS unit can undergo free diffusion, contributing to their high flowability at room temperature. The photoswitching viscoelasticity of GMs is further used for self-healing and photoswitchable adhesion. This work paves new pathways for the regulation of material viscoelasticity and the design of GM-based smart materials.

Exploration of Molecular Nanoparticles as Soft Structural Materials and Their Structure-Property Relationship.

The search for alternative chemical systems other than polymers with chain topologies for soft structural materials raises general interests in fundamental materials and chemical sciences. It is also appealing from an engineering perspective for the urgent need to resolve the typical trade-offs of polymer systems. Herein, a subnanometer molecular cluster, polyhedral oligomeric silsesquioxanes, is assembled into molecular nanoparticles (MNPs) with star topology. Broadly tunable viscoelasticity can be realized by fine-tuning the MNPs' deformability. Being analogous to polymeric systems, the hierarchical structural relaxation dynamics can be observed, and their relaxation time and temperature dependence are dominated by the linker flexibilities. This not only provides microscopic understanding on MNP's unique viscoelasticity but also offers enormous opportunities for modulating their mechanical properties via linker engineering. Our work proves the possibility of applying structural units with particle topologies for the design of soft structural materials.

Particle topology-regulated relaxation dynamics in cluster-ordering.

The granular materials of soft particles (SPs) demonstrate unique viscoelasticity distinct from general colloidal and polymer systems. Exploiting dynamic light scattering measurements, together with molecular dynamics simulations, we study the diffusive dynamics of soft particle clusters (SPCs) with spherical and cylindrical brush topologies, respectively, in the melts of SPs. A topologically constrained relaxation theory is proposed by quantitatively correlating the relaxation time to the topologies of the SPCs, through the mean free space (Va) of tethered SPs in the cluster. The tethered SPs in SPCs are crowded by SPs of the melts to form the cage zones, and the cooperative diffusion of the tether SPs in the zones is required for the diffusive motion of SPCs. The cage zone serves as an entropic barrier for the diffusion of SP clusters, while its strength is determined by Va. Three characteristic modes can be confirmed: localized non-diffusive mode around critical Va, diffusive mode with Va deviating far from the critical value, and a sub-diffusive mode as an interlude between two limits. Our studies raise attention to the emergent physical properties of materials based on SPs via a topological design while opening new avenues for the design of soft structural materials.

Unique Viscoelasticity and Hierarchical Relaxation Dynamics of Molecular Granular Materials.

Resulting from the dense packing of subnanometer molecular clusters, molecular granular materials (MGMs) are shown to maintain high elasticity far above their apparent glass transition temperature (Tg*). However, our microscopic understanding of their structure-property relationship is still poor. Herein, 1 nm polyhedral oligomeric silsesquioxanes (POSSs) are appended to a backbone chain in a brush configuration with different flexible linker chains. Assemblies of these brush polymers exhibit hierarchical relaxation dynamics with the glass transition arising from the cooperative dynamics of packed POSSs. The interaction among the assemblies can be strengthened by increasing the rigidity of linkers with the MGM relaxation modes changing from colloid- to polymer chain-like behavior, rendering their tunable viscoelasticity. This finally contributes to the decoupling of mechanical and thermal properties by showing elasticity dominant mechanical properties at a temperature 150 K above the Tg*.

Supramolecular Complexation of Metal Oxide Cluster and Non-Fluorinated Polymer for Large-Scale Fabrication of Proton Exchange Membranes for High-Power-Density Fuel Cells.

Cost-effective, non-fluorinated polymer proton exchange membranes (PEMs) are highly desirable in emerging hydrogen fuel cells (FCs) technology; however, their low proton conductivities and poor chemical and dimension stabilities hinder their further development as alternatives to commercial Nafion®. Here, we report the inorganic-organic hybridization strategy by facilely complexing commercial polymers, polyvinyl butyral (PVB), with inorganic molecular nanoparticles, H3 PW12 O40 (PW) via supramolecular interaction. The strong affinity among them endows the obtained nanocomposites amphiphilicity and further lead to phase separation for bi-continuous structures with both inter-connected proton transportation channels and robust polymer scaffold, enabling high proton conductivities, mechanical/dimension stability and barrier performance, and the H2 /O2 FCs equipped with the composite PEM show promising power densities and long-term stability. Interestingly, the hybrid PEM can be fabricated continuously in large scale at challenging ~10 µm thickness via typical tape casting technique originated from their facile complexing strategy and the hybrids' excellent mechanical properties. This work not only provides potential material systems for commercial PEMs, but also raises interest for the research on hybrid composites for PEMs.

Strain-Induced Heteromorphosis Multi-Cavity Cages: Tension-Driven Self-Expansion Strategy for Controllable Enhancement of Complexity in Supramolecular Assembly.

Coordinative supramolecular cages with adjustable cavities have found extensive applications in various fields, but the cavity modification strategies for multi-functional structures are still challenging. Here, we present a tension-driven self-expansion strategy for construction of multi-cavity cages with high structural complexity. Under the regulation of strain-induced capping ligands, unprecedented heteromorphosis triple-cavity cages S2 /S4 were obtained based on a metallo-organic ligand (MOL) scaffold. The heteromorphosis cages exhibited significant higher cavity diversity than the homomorphous double-cavity cages S1 /S3 ; all of the cages were thoroughly characterized through various analytical techniques including (1D and 2D) NMR, ESI-MS, TWIM-MS, AFM, and SAXS analyses. Furthermore, the encapsulation of porphyrin in the cavities of these multi-cavity cages were investigated. This research opens up new possibilities for the architecture of heteromorphosis supramolecular cages via precisely controlled "scaffold-capping" assembly with preorganized ligands, which could have potential applications in the development of multifunctional structures with higher complexity.

Polyoxometalate-Organic Hybrid "Calixarenes" as Supramolecular Hosts.

Calixarenes are among the most useful and versatile macrocycles in supramolecular chemistry. The one thing that has not changed in the 80 years since their discovery, despite numerous derivatizations, is their fully organic, covalent scaffolds. Here, we report a new type of organic-inorganic hybrid "calixarenes" constructed by means of coordination-driven assembly. Replacing acetate ligands on the {SiW10 Cr2 (OAc)2 } clusters with 5-hydroxyisophthalates allows these 95° inorganic building blocks to be linked into bowl-shaped, hybrid "calix[n]arenes" (n=3, 4). With a large concave cavity, the metal-organic calix[4]arene can accommodate nanometer-sized polyoxoanions in an entropically driven process. The development of hybrid variants of calixarenes is expected to expand the scope of their physicochemical properties, guest/substrate binding, and applications on multiple fronts.

Controllable and Reversible Assembly of Nanofiber from Natural Macromolecules via Protonation and Deprotonation.

Nanofiber is the critical building block for many biological systems to perform various functions. Artificial assembly of molecules into nanofibers in a controllable and reversible manner will create "smart" functions to mimic those of their natural analogues and fabricate new functional materials, but remains an open challenge especially for nature macromolecules. Herein, the controllable and reversible assembly of nanofiber (CSNF) from natural macromolecules with oppositely charged groups are successfully realized by protonation and deprotonation of charged groups. By controlling the electrostatic interaction via protonation and deprotonation, the size and morphology of the assembled nanostructures can be precisely controlled. A strong electrostatic interaction contributes to large nanofiber with high strength, while poor electrostatic interaction produces finer nanofiber or nanoparticle. And especially, the assembly, disassembly, and reassembly of the nanofiber occurs reversibly through protonation and deprotonation, thereby paving a new way for precisely controlling the assembly process and structure of nanofiber. The reversible assembly allows the nanostructure to dynamically reorganize in response to subtle perturbation of environment. The as-prepared CSNF is mechanical strong and can be used as a nano building block to fabricate high-strength film, wire, and straw. This study offers many opportunities for the biomimetic synthesis of new functional materials.

Spatiotemporal Studies of Soluble Inorganic Nanostructures with X-rays and Neutrons.

This Review addresses the use of X-ray and neutron scattering as well as X-ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub-Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal-organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small- and wide-angle X-ray or neutron scattering), 2) PDF (pair-distribution function analysis of X-ray total scattering), and 3) XANES and EXAFS (X-ray absorption near-edge structure and extended X-ray absorption fine structure, respectively). While the scattering techniques provide structural information, X-ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.

The Coordination Nanocages-Integrated Polymer Brush Networks for Flexible Microporous Membranes with Exceptional H2 /CO2 Separation Performance.

The emergence of polymers with intrinsic microporosity provides solutions for flexible gas separation membranes with both high gas permeability and selectivity. However, their applications are significantly hindered by the costly synthetic efforts, limited availability of chemical systems, and narrow window of microporosity sizes. Herein, flexible mixed matrix membranes with tunable intrinsic microporosity can be facilely fabricated from the coordination assembly of polymer brushes and coordination nanocages. Polymer brushes bearing isophthalic acid side groups can coordinate with Cu2+ to assemble into polymer networks crosslinked by 2 nm nanocages. The semi-flexible feature of the polymer brush and the high crosslinking density of the network prevent the network from collapsing during solvent removal and the obtained aerogels demonstrate hierarchical structure with dual porosity from the crosslinked polymer network and coordination nanocage, respectively. The porosity can be facilely tuned via the amount of Cu2+ by regulating the network crosslinking density and nanocage loadings, and finally, optimized gas separation that surpasses Robeson upper bound for H2 /CO2 can be achieved. The coordination-driven assembly protocol paves a new avenue for the cost-effective synthesis of polymers with intrinsic microporosity and the fabrication of flexible gas separation membranes.

Modulating Ligand-Exchange Dynamics on Metal-Organic Polyhedra for Reversible Sorting and Hybridization of Miktoarm Star Polymers.

The precise synthesis of miktoarm star polymers (MSPs) remains one of the great challenges in synthetic chemistry due to the difficulty in locating appropriate structural templates and polymer grafting/growing strategies with high selectivity and efficiency. Herein, ≈2 nm metal-organic polyhedra (MOPs), constructed from the coordination of isophthalic acid (IPA) and Cu2+ , are applied as templates for the precise synthesis of 24-arm MSPs for their unique logarithmic ligand-exchange dynamics. Six different polymers are prepared with IPA as an end group and they further coordinated with Cu2+ to afford the corresponding 24-arm star homo-polymers. MSPs can be obtained by mixing targeted homo-arm star polymers in solutions upon thermal annealing. The compositions of MSPs can be facilely and precisely tuned by the recipe of the star polymer mixtures used. Interestingly, the obtained MSPs can be sorted into homo-arm star polymers through a typical solvent extraction procedure. The hybridization and sorting process can be reversibly conducted through the cycle of thermal annealing and solvent treatment. The complex coordination framework not only opens new avenues for the facile and precise synthesis of MSPs and MOPs with hybrid functionalities, but also provides the capability to design sustainable polymer systems.

Correlation of Structure and Dynamics Behavior in Polyzwitterions: From Concentrated Solution to Gel-Like State.

The dynamic behaviors of polyzwitterions, poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate) (PSBP), are investigated using dynamic light scattering, small angle X-ray scattering, and rheology.  The findings reveal two relaxation modes, including a fast and a slow mode, which  are observed in both solution state and gel-like state, with varying polyzwitterion concentration (CP ) and NaCl concentration (CNaCl ). As CP and CNaCl increasing, a slower slow mode and a faster fast mode are observed. The fast mode corresponds to the diffusion of chains, while the slow mode arises from chain aggregations. In solutions, the slow mode is dominated by the diffusion of chain aggregations. However, in the gel-like state, the "cage network" traps aggregations more densely, leading to their dynamic behavior being dominated by enhanced topological entanglements and ionic interactions. This difference highlights the unique nature of the slow relaxation mode between concentrated solution and gel-like state, arising from changes in the average distance between chain aggregations resulting from increased CP and CNaCl concentrations.

Molecular Complexation of Polymers and Metal Oxide Clusters for Semicrystalline, Thermoplastic Anhydrous Proton Exchange Membranes in Fuel Cells.

With the manipulation of surface charges and loadings, 1 nm super-acidic metal oxide clusters can co-crystallize with poly(ethylene glycol) (PEG) at molecular scale for thermoplastic anhydrous proton exchange membranes (PEMs). The coexistence of crystalline and amorphous regions endows the PEMs with a high Young's modulus and high flexibility, while the noncovalent complex interactions enable facile preparation and (re)processing. Furthermore, the diffusive dynamics of PEG chains is slowed by the confinement effect, while the local segmental dynamics is accelerated due to the transition of the chain conformation from helix to zigzag when confined in the crystalline framework. This greatly facilitates proton transportation in the crystalline region for an excellent anhydrous proton conductivity of 4.5 × 10-3 S cm-1 at 90 °C. The balanced proton conductivity, mechanical strength, and processability of the PEMs contribute to the promising power density of H2/O2 fuel cells assembled with co-crystalline PEMs at high temperatures under dry conditions.

Scalable synthesis of soluble crystalline ionic-graphdiyne by controlled ion expansion.

Graphdiyne (GDY) is a promising material possessing extensive electronic tunability, high π conjugacy, and ordered porosity at a molecular level for the sp/sp2-hybridized periodic structures. Despite these advantages, the preparation of soluble and crystalline graphdiyne is limited by the relatively compact stacking interactions, mostly existing in thick-layer and insoluble solids. Herein, we proposed a strategy of "framework charge-induced intercalation (FCII)" for the synthesis of a soluble (4.3 mg ml-1) and yet interlayer-expanded (∼0.6 Å) crystalline ionic graphdiyne, named as N+-GDY, through regulating the interlayer interactions. The skeleton of such a sample is positively charged, and then the negative ions migrate to the interlayer to expand the space, endowing the N+-GDY with solution processability. The crystal structure of N+-GDY is proved through analysis of HR-TEM images under different axes of observation and theoretical simulations. The resulting N+-GDY possesses high dispersity in organic solvents to produce a pure-solution phase which is conducive to the formation of oriented N+-GDY films, accompanied by exfoliation-nanosheet restacking. The film exhibits a conductivity of 0.014 S m-1, enabling its applications in electronic devices.

Functional Molecular Granular Materials: Advances and Perspectives.

Molecular granular materials (MGMs) are constructed with sub-nanoscale molecular clusters (MCs) as the building units and they have recently been observed to possess enriched functionalities distinct from granular materials of colloid nanoparticles. Herein, the birth and recent research advances in MGMs are summarized with the topics covering the precise synthesis of MC assemblies with target topologies, the hierarchical relaxation dynamics and tuneable viscoelasticity, impact-resistant capacity, and proton conductivity performance. The extremely small size of MC renders them two features: bulk diffusive dynamics with energy scale close to thermal fluctuation energy and the dominant volume fraction of surface structures. This finally leads to the hierarchical relaxation dynamics and broadly tuneable viscoelasticity of MGMs although the structural units are with small sizes and low Mw . Therefore, MGMs have been applied as impact resistant materials and proton conductors for the highly tuneable relaxation dynamics.

Supramolecular Assembly and Microscopic Dynamics Modulation of Nanoscale Inorganic Cryptand and Polymer Complex for Versatile Design of Flexible Single-Ion Conductors.

The popular design of solid-state electrolytes (SSEs) from the chain relaxation of polymers faces the trade-offs among ion conductivity, stability, and processability. Herein, 2 nm inorganic cryptand molecules with the capability to carry different types of cations, including Ag+, Na+, K+, and Ca2+, are complexed with cationic polymers via ionic interaction, respectively, and the hybrid materials further phase separate into lamellar or hexagonal columnar structures. The successful establishment of ordered structures with ion channels from the packing of inorganic cryptands confers SSEs' excellent ionic conductivity to versatile types of cations. Meanwhile, suggested from the combination of broad dielectric spectroscopy, rheology, and thermal analysis, the fast chain relaxation can activate the dynamics of inorganic cryptand molecules and facilitate the ion hopping process in ion channels. The supramolecular interaction in the complex enables the highly flexible physical appearance for defect-free contact with electrodes as well as cost-effective processability and recyclability.

Probing sub-5 Ångstrom micropores in carbon for precise light olefin/paraffin separation.

Olefin/paraffin separation is an important but challenging and energy-intensive process in petrochemical industry. The realization of carbons with size-exclusion capability is highly desirable but rarely reported. Herein, we report polydopamine-derived carbons (PDA-Cx, where x refers to the pyrolysis temperature) with tailorable sub-5 Å micropore orifices together with larger microvoids by one-step pyrolysis. The sub-5 Å micropore orifices centered at 4.1-4.3 Å in PDA-C800 and 3.7-4.0 Å in PDA-C900 allow the entry of olefins while entirely excluding their paraffin counterparts, performing a precise cut-off to discriminate olefin/paraffin with sub-angstrom discrepancy. The larger voids enable high C2H4 and C3H6 capacities of 2.25 and 1.98 mmol g-1 under ambient conditions, respectively. Breakthrough experiments confirm that a one-step adsorption-desorption process can obtain high-purity olefins. Inelastic neutron scattering further reveals the host-guest interaction of adsorbed C2H4 and C3H6 molecules in PDA-Cx. This study opens an avenue to exploit the sub-5 Å micropores in carbon and their desirable size-exclusion effect.

The counterion-mediated controllable coacervation of nano-ions with polyelectrolytes.

Nano-ions can complex with polyelectrolytes for coacervates with hierarchical structures; however, the rational design of functional coacervations is still rare due to the poor understanding of their structure-property relationship from their complex interaction. Herein, 1 nm anionic metal oxide clusters, PW12O403-, with well-defined, mono-disperse structures are applied to complex with cationic polyelectrolyte and the system shows tunable coacervation via the alternation of counterions (H+ and Na+) of PW12O403-. Suggested from Fourier transform infrared spectroscopy (FT-IR) and isothermal titration studies, the interaction between PW12O403- and cationic polyelectrolytes can be modulated by the bridging effect of counterions via hydrogen bonding or ion-dipole interaction to carbonyl groups of polyelectrolytes. The condensed structures of the complexed coacervates are explored by small angle X-ray and neutron scattering techniques, respectively. The coacervate with H+ as counterions shows both crystallized and discrete PW12O403- clusters, with a loose polymer-cluster network in comparison to the system of Na+ which shows a dense packing structure with aggregated nano-ions filling the meshes of polyelectrolyte networks. The bridging effect of counterions helps understand the super-chaotropic effect observed in nano-ion system and provides avenues for the design of metal oxide cluster-based functional coacervates.

Metal oxide cluster-assisted assembly of anisotropic cellulose nanocrystal aerogels for balanced mechanical and thermal insulation properties.

Cellulose nanocrystal (CNC) materials grant abundant possibilities for insulation, however, their extensive application is hindered by the intrinsic tradeoff between their thermal insulating performance and mechanical properties. Here, we show that CNC aerogels with balanced thermal and mechanical performance can be fabricated via a 1 nm metal oxide cluster (phosphotungstic acid, PTA)-assisted unidirectional freeze-drying processing. The as-prepared hybrid aerogels with hierarchical porous structures consisting of layer-by-layer CNC nanosheets enable the decoupling of the strengthening of mechanical properties and the enhancement of thermal insulating capabilities. Within layered structures, the surface-doped nanosized PTA clusters with negative charges behave as dynamic physical cross-linking points, and continuous networks of PTA-doped CNC can be formed via multiple supramolecular interactions (e.g., electrostatic attractions and hydrogen bonds). The afforded stable three-dimensional network structures are able to withstand externally applied forces and large deformations, endowing the aerogels with excellent mechanical performance. Moreover, the inter-layer gap is dominated by nanopores, endowing much lower thermal conductivities along the radial direction in comparison to the axial direction. The addition of PTA clusters also contributes to the obvious enhancements of the fire-retardant properties. Our discoveries provide a facile approach for the design and scalable production of CNC-based insulation materials with optimized mechanical properties and additional fire-retardant properties.