Supramolecular Complexation Reinforced Polymer Frustrated Packing: Controllable Dual Porosity for Improved Permselectivity of Coordination Nanocage Mixed Matrix Membranes.

The developments of mixed matrix membranes (MMMs) are severely hindered by the complex inter-phase interaction and the resulting poor utilization of inorganics' microporosity. Herein, a dual porosity framework is constructed in MMMs to enhance the accessibility of inorganics' microporosity to external gas molecules for the effective application of microporosity for gas separation. Nanocomposite organogels are first prepared from the supramolecular complexation of rigid polymers and 2 nm microporous coordination nanocages (CNCs). The network structures can be maintained with microporous features after solvent removal originated from the rigid nature of polymers, and the strong coordination and hydrogen bond between the two components. Moreover, the strong supramolecular attraction reinforces the frustrated packing of the rigid polymers on CNC surface, leading to polymer networks' extrinsic pores and the interconnection of CNCs' micro-cavities for the fast gas transportation. The gas permeabilities of the MMMs are 869 times for H2 and 1099 times for CO2 higher than those of pure polymers. The open metal sites from nanocage also contribute to the enhanced gas selectivity and the overall performance surpasses 2008 H2/CO2 Robeson upper bound. The supramolecular complexation reinforced packing frustration strategy offers a simple and practical solution to achieve improved gas permselectivity in MMMs.

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.

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*.

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.

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.

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.

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.

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.

Decoupling Segmental Dynamics and Ionic Transport for Superionic Anhydrous Proton Conductors of Polyoxometalate-poly(ethylene glycol) Nanocomposites.

Superionic anhydrous proton conductors can be obtained from the complexation of nanoscale polyoxometalates (POMs) and poly(ethylene glycol) (PEG) in the "polymer in salt" regime. The reduced energy barrier of H+ hopping is facilitated from the increased H+ concentration and shortened inter-POM distances. POMs with identical structure/size (≈1 nm) but different charge densities are complexed with PEG, respectively, with concentrations ranging from 10 to 60 % wt. Increasing trends of viscosities can be observed with the rising charge densities of POMs due to the increasing confinement strength on PEG substrate from POMs. Fractional Walden rule is further applied to analyze the viscosity and proton conductivity correlations, and microscopic mechanisms of proton conduction for PEG-POM nanocomposites are revealed: 1) ion transport is highly associated with polymer chain dynamic for POMs concentrations ranging from 10 to 30 % wt.; 2) ionic conduction is largely decoupled from chain dynamic of polymer matrix for concentrations ranging from 40 to 60 % wt. with Walden plots shifted to the superionic regime. The decoupling of proton transport from polymer segment dynamics allows the simultaneous enhancements of the nanocomposites' mechanical properties and proton conductions, providing guidelines for the rational design of anhydrous proton conductors with integrated functionalities.

Dynamics and Proton Conduction of Heterogeneously Confined Imidazole in Porous Coordination Polymers.

The nanoconfinement of proton carrier molecules may contribute to the lowing of their proton dissociation energy. However, the free proton transportation does not occur as easily as in liquid due to the restricted molecular motion from surface attraction. To resolve the puzzle, herein, imidazole is confined in the channels of porous coordination polymers with tunable geometries, and their electric/structural relaxations are quantified. Imidazole confined in a square-shape channels exhibits dynamics heterogeneity of core-shell-cylinder model. The core and shell layer possess faster and slower structural dynamics, respectively, when compared to the bulk imidazole. The dimensions and geometry of the nanochannels play an important role in both the shielding of the blocking effect from attractive surfaces and the frustration filling of the internal proton carrier molecules, ultimately contributing to the fast dynamics and enhanced proton conductivity.

Controllable gelation of coordination nanocages from the physical interactions among surface grafted cholesteryl groups.

Coordination nanocage (CNC) incorporated gels have attracted enormous attention for the effective integration of micro-porosity, mechanical flexibility and processability; however, the understanding of their microscopic structure-property relationships remains unclear. Herein, CNCs with 24 surface grafted cholesterol groups are constructed precisely and their gelation can be manipulated upon the tunning of solvent polarities. Optically homogeneous organogels can be formed by introducing a certain amount of bad solvents into the solutions of hairy CNCs and the gelation can be reversed through temperature variation. Suggested from scattering and molecular dynamics studies, the solvophobic interaction-driven aggregation of cholesterol units contributes to the physical crosslinking of CNCs and finally the gelation of CNC solutions. The mechanical strength of the obtained gels is observed to be highly dependent on the flexibility of the organic linkers that bond the cholesterol units on the CNC surface. The effective interaction and dense packing of the cholesterol units in their aggregates highly rely on the degree of freedom of the cholesterol, which is controlled by the flexibility of the organic linkers that bond them on the CNC surface. The observed viscoelastic performance accompanied by the well-controlled mechanical strength of the organogels unambiguously demonstrates the potential for exploiting the synergistic physical correlations to fabricate novel functional materials from CNCs.

Surface Functionality-Regulated and Entropy-Driven Thermodynamics of the Formation of Coordination Nanocages.

Coordination nanocages (CNCs) are under intense research in nanoscience and supramolecular chemistry for their enriched surface functionalities and micro-porosity; however, the understanding of their formation mechanism is still poor due to the difficulty in probing their solution structures. Herein, the CNC formation process from the coordination complexation of the macromolecular isophthalic acid (IPA) ligand and Cu2+ is studied via isothermal titration calorimetry, and its entropy-driven feature is revealed to be originated from the collapse of solvation layers of the assembly units. The CNC formation is thermodynamically less favored with smaller binding constants when the sizes of macromolecular IPA ligands are larger, which originated from the space crowding of macromolecules of the ligands on CNC surfaces and the resulting entropy loss of polymer chain conformations. Meanwhile, the chemical equilibrium of CNC formation can be tuned upon altering the Cu2+/IPA ratio, and the yield of CNCs, suggested from size exclusion chromatography studies, decreases when excessive Cu2+ is applied, providing guidelines for CNC design and synthesis.

Unique Dynamics of Hierarchical Constrained Macromolecular Ligands on Coordination Nanocage Surface Promotes Facile and Precise Assembly of Polymers.

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.

Unique Dynamics of Water Confined on the Surface of Metal Oxide Clusters.

Water confined on metal oxide surface plays significant roles in heterogeneous catalysis. Heteropolyacid, a 1.2 nm-metal oxide cluster with well-defined structure, is applied as a model to understand the dynamics of water on its surface. The surface water strongly associates with heteropolyacid cluster and form the so-called 'pseudoliquid phase' where catalytic reactions are conducted. Broadband dielectric spectroscopy and differential scanning calorimetry have been applied to probe the dynamics of water in this pseudoliquid phase. A supercooling phase transition of water below its normal melting temperature and a dipolar glassy relaxation behaviour due to the hindered dynamics of water have been observed. The rich dynamic behavior on the surface of such well-defined metal clusters provide new perspectives to understand the properties of surface water and their relation to catalytic performance of heteropolyacid.

The Microscopic Structure-Property Relationship of Metal-Organic Polyhedron Nanocomposites.

Monodispersed hairy nanocomposites with typical 2 nm (isophthalic acid)24 Cu24 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.