Coordination Nanocage Research Articles

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 2nm 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.

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 2nm 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.

Microscopic mechanism of gas transport in mixed matrix membranes of coordination nanocages

The strong inter-phase attraction is required for the effective and stable integration of inorganics and polymers in mixed matrix membranes (MMMs), which would impact the structures and microscopic dynamics of the two phases and cause unexpected deviation of MMM performance from original design; however, the understanding of its structure-property relationship is still poor. Herein, 2 nm coordination nanocage (CNC) with well-defined, monodispersed structure is complexed with poly(4-vinyl pyridine-r-n-butyl acrylate) (P4VP-co-PnBA) via both coordination and hydrogen bonding to afford model systems. The surface interaction between the two phases is quantified by the thickness of absorbed layers of polymers on CNC surface as well as the segmental dynamics of polymers. In broadband dielectric spectroscopy (BDS) studies, accelerated chain dynamics can be observed in the nanocomposites with loadings of CNC, which is originated from the frustrated packing of polymers absorbed on CNC surface. The co-effect of interfacial layer thickness and chain dynamics leads to the non-monotonic dependence of the MMMs’ gas permeabilities on CNC concentrations. The temperature dependence of their gas permeability and chain dynamics are both explored and the two processes are fully decoupled at temperatures higher than 333 K due to the weakening of multiple supramolecular interaction. Our discoveries provide microscopic and quantitative understanding on structure-property relationship of MMMs, which benefits directly to the rational design of polymer structures for optimized gas separation performance.

Coordination-directed self-assembly of nano-cages: metal ion-change, ligand-extending, shape-control and transdermal drug delivery.

The combination of different pyridyl ligands and metal ions has proven to be a very reliable strategy for controlling the coordination mode of the heterometallic coordination nano-cages. Adjusting the length of the ligands could result in the selective synthesis of several heterometallic coordination nano-cages, either [8Rh + 2M]-4L, [8Rh + 2M]-5L or [8Rh + 4M]-6L cages, derived from the very same precursors (LH3tzdc) through half-sandwich rhodium self-assembly. Moreover, a series of [8Rh + 4M]-6L cages was chosen to exemplify the preparation. The rigidity of various pyridyl donor ligands caused the vertical nano-cage to be energetically preferred and was able to change the self-assembly process through ligand flexibility to selectively give the inclined nano-cage and cross nano-cage.

A Discrete 3d–4f Metallacage as an Efficient Catalytic Nanoreactor for a Three-Component Aza-Darzens Reaction

The exploration and development of coordination nanocages can provide an approach to control chemical reactions beyond the bounds of the flask, which has aroused great interest due to their significant applications in the field of molecular recognition, supramolecular catalysis, and molecular self-assembly. Herein, we take the advantage of a semirigid and nonsymmetric bridging ligand (H5L) with rich metal-chelating sites to construct an unusual and discrete 3d-4f metallacage, [Zn2Er4(H2L)4(NO3)Cl2(H2O)]·NO3·xCH3OH·yH2O (Zn2Er4). The 3d-4f Zn2Er4 cage possesses a quadruple-stranded structure, and all of the ligands wrap around an open spherical cavity within the core. The self-assembly of the unique cage not only ensures the structural stability of the Zn2Er4 cage as a nanoreactor in solution but also makes the bimetallic lanthanide cluster units active sites that are exposed in the medium-sized cavity. It is important to note that the Zn2Er4 cage as a homogeneous catalyst has been successfully applied to catalyze three-component aza-Darzens reactions of formaldehyde, anilines, and α-diazo esters without another additive under mild conditions, displaying better catalytic activity, higher specificity, short reaction time, and low catalyst loadings. A possible mechanism for this three-component aza-Darzens reaction catalyzed by the Zn2Er4 cage has been proposed. These experimental results have demonstrated the great potential of the discrete 3d-4f metallacage as a host nanoreactor for the development of supramolecular or molecular catalysis.

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.

Modulating Polymer Dynamics via Supramolecular Interaction with Ultrasmall Nanocages for Recyclable Gas Separation Membranes with Intrinsic Microporosity.

The engineering of mixed-matrix membranes is severely hindered by the trade-off between mechanical performance and effective utilization of inorganic fillers' microporosity. Herein, we report a feasible approach for optimal gas separation membranes through the fabrication of coordination nanocages with poly(4-vinylpyridine) (P4VP) via strong supramolecular interactions, enabling the homogeneous dispersion of nanocages in polymer matrixes with long-term structural stability. Meanwhile, suggested from dynamics studies, the strong attraction between P4VP and nanocages slows down polymer dynamics and rigidifies the polymer chains, leading to frustrated packing and lowered densities of the polymer matrix. This effect allows the micropores of nanocages to be accessible to external gas molecules, contributing to the intrinsic microporosity of the nanocomposites and the simultaneous enhancement of permselectivities. The facile strategy for supramolecular synthesis and polymer dynamics attenuation paves avenues to rational design of functional hybrid membranes for gas separation applications.

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.

Self-Assembled Pd12 Coordination Cage as Photoregulated Oxidase-Like Nanozyme.

Designing supramolecular architectures with uncommon geometries embedded with functional building units is of immense importance in contemporary research. In this report, we present a new water-soluble Pd12L6 supramolecular coordination nanocage (1) that was synthesized via self-assembly of a tetradentate donor (L) with ditopic acceptor cis-[(en)Pd(NO3)2] [en = ethylenediamine]. Self-assembly of a tetratopic donor with a cis-blocked 90° acceptor commonly produces tri/tetra- or hexagonal barrel-type structures. However, the resulting cage 1 has an uncommon geometry consisting of two triangular cupolas conjoined through an irregular common hexagonal base. Incorporation of the benzothiadiazole unit in the structure helped in the photogeneration of reactive oxygen species (ROS) in water. Many nanomaterials have shown to have the ability to mimic the catalytic activity of natural enzymes (nanozymes). Majority of such nanozymes are water insoluble metal/metal-oxide nanoparticles or extended metal organic frameworks (MOFs)/metal-carbon composites, etc. The present water-soluble Pd12 nanocage 1 has shown excellent oxidase-like activity upon irradiation with white light. The enzymatic activity of 1 is photoregulated which offers other obvious advantages, such as external control of enzymatic activity and noninvasiveness. The oxidase-like activity and exogenous ROS generation have been further exploited in photocatalytic antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) bacterial strain.

Actinide Separation Inspired by Self-Assembled Metal-Polyphenolic Nanocages.

The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides, and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely, nanoextraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U24-based hexameric pyrogallol[4]arene nanocages with distinctive [U2(PG)2] binuclear units (PG = pyrogallol) that rapidly assembled in situ in monophasic solvent were identified by single-crystal X-ray diffraction, MALDI-TOF mass spectrometry, NMR spectroscopy, and small-angle X-ray and neutron scattering. Comprehensive biphasic extraction studies showed that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, thereby demonstrating its potential for efficient separation of actinide ions.

Hybrid Uranyl-Phosphonate Coordination Nanocage.

We report herein a general synthetic approach for designing uranyl coordination cages. Compounds 1 and 2 are constructed through a temperature-dependent and solvent-driven self-assembly. In both cases, the synthetic strategy involves in situ phosphonate ligand condensation into a flexible pyrophosphonate ligand. This pyrophosphonate ligand formation is essential for the introduction of curvature into these compounds. In the presence of PF6- ions that are derived from hydrofluoric acid, a macrocyclic uranyl-phosphonate discrete compound, 1, whose cavity contains PF6- ions, hydronium ions, and water molecules, is obtained. When Cs+ cations are used in the synthesis, a remarkable uranyl coordination nanocage, 2, resulted. The macrocycle (1) is approximately 10.9 × 10.9 Å2 in diameter while the nanocage (2) is approximately 15.0 × 11.3 Å2 in diameter, as measured from the outer oxygen atoms of the uranyl centers. Both compounds are constructed from a UO22+ moiety, coordinated by an additional four oxygen atoms from the phosphonate group to form pentagonal bipyramidal geometry. All the compounds fluoresce at room temperature, showing characteristic vibronically coupled charge-transfer based emission.

Metal-Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis.

We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal-organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition-fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were grafted from the MOP core. On the other hand, the convergent route provided identical CSP architectures by simple mixing of a macroligand and copper ions. Isophthalic acid-terminated polymers (so-called macroligands) immediately formed the corresponding CSPs through a coordination reaction with copper(II) ions. This convergent route enabled us to obtain miktoarm CSPs with tunable chain compositions through ligand mixing alone. This powerful method allows instant access to a wide variety of multicomponent star polymers that conventionally have required highly skilled and multistep syntheses. MOP-core CSPs are a new class of star polymer that can offer a design strategy for highly processable porous soft materials by using coordination nanocages as a building component.

Generalized Synthesis of Calixarene-Based High-Nuclearity M4n Nanocages (M = Ni or Co; n = 2–6)

A family of high-nuclearity M4n (M = Ni or Co, n = 2–6) coordination nanocages constructed by M4–calix[4]arene molecular building blocks (MBBs) with inorganic phosphate or organic phosphonate ligands have been isolated by solvothermal syntheses and characterized by single-crystal X-ray diffraction. This family can be divided into five structural types with an increase in the number of M4–calix[4]arene MBBs, including Ni8 (1 and 2, n = 2), M12 (M = Ni (3) and Co (4), n = 3), M16 (M = Ni (5) and Co (6), n = 4), Co20 (7, n = 5), and Co24 (8, n = 6) coordination nanocages. Structural analyses reveal that the metallic cores of 1 and 2 are arranged in chair conformation, while compounds 3–6 with closed-shell structures, where their ports are sealed by sodium ions, present the first examples of 2p-3d heterometallic metal–calixarene nanocages to our knowledge. The novel helmet-like Co20 (7) is the only one in this family with an open-shell structure, which can be thought of as a truncated octahedral Co24 (8) nano...

A tetragonal prismatic {Co32} nanocage based on thiacalixarene

A novel coordination nanocage was obtained with in situ-generated tetrazole ligands from the cobalt-thiacalix[4]arene system. Four in situ-generated 1,3-bis(2H-tetrazol-5-yl)benzene ligands bolster eight Co4-calix shuttle-cock-like secondary building units (SBUs) into a hollow tetragonal prism with a high surface area. The unprecedented {Co32} nanocage presents the highest nuclearity example.

Two 2D metal–calixarene aggregates incorporating pre-designed coordination nanocages

Two 2D metal-calixarene aggregates were designed and assembled by M4-TC4A (M = Fe, Co; TC4A = p-tert-butylthiacalix[4]arene) SBUs and {MCl2} units with isonicotinic acid molecules, which presents a possible way to build the extended metal-calixarene assemblies incorporating pre-designed nanocages using multifunctional linkers.

Protein encapsulation within synthetic molecular hosts

Protein encapsulation has long attracted many chemists and biologists because of its potential to control the structure and functions of proteins, but has been a daunting challenge because of their incommensurably larger size compared with common synthetic hosts. Here we report the encapsulation of a small protein, ubiquitin, within giant coordination cages. The protein was attached to one bidentate ligand and, upon addition of Pd(II) ions (M) and additional ligands (L), M(12)L(24) coordination nanocages self-assembled around the protein. Because of the well-defined host framework, the protein-encapsulated structure could be analysed by NMR spectroscopy, ultracentrifugation and X-ray crystallography.

Dual lanthanide role in the designed synthesis of hollow metal coordination (Prussian Blue analogue) nanocages with large internal cavity and mesoporous cage

Prussian Blue (PB) analogue metal coordination nanocages comprised of mesoporous walls (ca. 3.5 nm pore width) encapsulating a cavity approaching ca. 100 nm in diameter (surfactant free) are presented as an advance in rational metal coordination polymer nanostructure design. The synthesis employs lanthanide ions (Gd(3+) or Er(3+)) which function initially as peripheral coordination crosslinkers of metallo-surfactant templated miniemulsion droplets, and, subsequently, as promoters in the removal of the organic component of those surfactants via metal-assisted ester hydrolysis. The success of this synthetic strategy relies entirely on the periphery coordination event occurring prior to the ester hydrolysis surfactant removal step. Crucially, this one-pot sequential synthesis was achieved using a newly developed metallo-surfactant designed to have a reduced ester hydrolysis rate. Syntheses of this innovative metallo-surfactant, intermediary PB analogue coordination polymer organo-nanoshells and the subsequent conversion to hollow metal coordination nanocages are fully characterised using a wide variety of techniques, including TEM, SEM, EFTEM, EDX, TGA, WAXD, NMR, N(2) adsorption, etc., and represent the first designed synthesis of hollow metal coordination nanocages containing a large nanoscale cavity (wall of hollow nanosphere is mesoporous; hence nanocage).

Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery

Porous coordination nanocages covered with alkyne groups are synthesized through judicious selection of the ligand and reaction conditions. The surface functionalization via click reaction with azide-terminated polyethylene glycol turns them into water-stable colloids, which exhibit controlled release of an anticancer drug 5-fluorouracil.

Thermosensitive gating effect and selective gas adsorption in a porous coordination nanocage

A porous coordination nanocage functionalized with 24 triisopropylsilyl groups exhibits a remarkable thermosensitive gate opening phenomenon and demonstrates a molecular sieving effect at a certain temperature range, which can be used for gas separation purposes.