Metal-organic Cages Research Articles

In vivo biodistribution of kinetically stable Pt2L4 nanospheres that show anti-cancer activity.

There is an increasing interest in the application of metal-organic cages (MOCs) in a biomedicinal context, as they can offer non-classical distribution in organisms compared to molecular substrates, while revealing novel cytotoxicity mechanisms. Unfortunately, many MOCs are not sufficiently stable under in vivo conditions, making it difficult to study their structure-activity relationships in living cells. As such, it is currently unclear whether MOC cytotoxicity stems from supramolecular features or their decomposition products. Herein, we describe the toxicity and photophysical properties of highly-stable rhodamine functionalized platinum-based Pt2L4 nanospheres as well as their building blocks under in vitro and in vivo conditions. We show that in both zebrafish and human cancer cell lines, the Pt2L4 nanospheres demonstrate reduced cytotoxicity and altered biodistribution within the body of zebrafish embryos compared to the building blocks. We anticipate that the composition-dependent biodistribution of Pt2L4 spheres together with their cytotoxic and photophysical properties provides the fundament for MOC application in cancer therapy.

A silver metal-organic cage with antibacterial activity for wound healing.

Bacterial infection is one of the most threatening diseases in humans and can result in tissue necrosis, inflammation, and so on. Although a large number of antibacterial materials have been developed, there are still some disadvantages in this field, including decreasing antibacterial activity in the aqueous solution or a short duration of time. Herein, a metal-organic cage named Ag-TBI-TPE with excellent antibacterial activity was prepared and applied in wound healing. Owing to the photosensitive production of the toxic ROS species and the positive charge of the surface, the Ag-TBI-TPE cage exhibits high antibacterial activity, especially under UV irradiation. It could accelerate the healing process of the infected wounds in vivo with satisfactory biocompatibility and bio-safety. The results indicated that after treatment with the Ag-TBI-TPE cage, with and without UV irradiation, the healing rates of wounds infected by E. coli and S. aureus were 89.59% and 93.05%, and 83.48% and 90.84%, respectively, which were much higher than those shown by the positive control group at 51.38% and 67.74%, respectively. This study not only sheds light on a design idea for a new antibacterial material but also further expands the potential application field of metal-organic cages.

Connecting metal–organic cages (MOCs) for CO2 remediation

The connection of metal organic cages (MOCs) via coordination driven bonds, covalent bonds or mechanical bonds yields functional materials at the interface between solid and liquid states with potential applications in CO2 remediation.

A 5.3 nm giant metal-organic cage and its supramolecular gel for the formation of dye molecular ionic pairs.

A terpyridine-based supramolecular cage was successfully synthesized by the self-assembly of a hexapodal metal-organic ligand with Zn2+. This metallo-cage exhibited two large parallel planes on the top and bottom with diameters close to 6 nm and a face-to-face distance close to 3.5 nm, thus possessing a large cavity. Electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR), two-dimensional nuclear Overhauser (2D-NOESY), and diffusion-ordered (DOSY) spectroscopies as well as transmission electron microscopy (TEM) and atomic force microscopy (AFM) measurements, unambiguously supported the formation of a supramolecular cage. Furthermore, the corresponding metal-organic gel was felicitously prepared in CH3CN/H2O and displayed good adsorption performance for dye molecules.

Highly efficient Förster resonance energy transfer between an emissive tetraphenylethylene-based metal-organic cage and the encapsulated dye guest.

The host-guest strategy presents an ideal way to achieve efficient Förster resonance energy transfer (FRET) by forcing close proximity between an energy donor and acceptor. Herein, by encapsulating the negatively charged acceptor dyes eosin Y (EY) or sulforhodamine 101 (SR101) in the cationic tetraphenylethene-based emissive cage-like host donor Zn-1, host-guest complexes were formed that exhibit highly efficient FRET. The energy transfer efficiency of Zn-1⊃EY reached 82.4%. To better verify the occurrence of the FRET process and make full use of the harvested energy, Zn-1⊃EY was successfully used as a photochemical catalyst for the dehalogenation of α-bromoacetophenone. Furthermore, the emission color of the host-guest system Zn-1⊃SR101 could be adjusted to exhibit bright white-light emission with the CIE coordinates (0.32, 0.33). This work details a promising approach to enhance the efficiency of the FRET process by the creation of a host-guest system between the cage-like host and dye acceptor, thus serving as a versatile platform for mimicking natural light-harvesting systems.

Imparting structural robustness of metal-organic cages based on oxo-dimolybdenum clusters.

A family of robust and stable molybdenum-based metal-organic cages have been obtained based on the [Mo2O2(μ2-O)2]2+ secondary building unit. The resulting cages are decorated with different pyrdine derivatives that impart structural stability, resulting in the structural elucidation of the activated cage with single-crystal diffraction. The chemical robustness of the cage is also demonstrated by the post-synthetic modification of the cage, which allows the exchange of the pyridine derivatives without rupture of the cage.

Zirconium metal-organic cage decorated with squaramides imparts dual activation for chemical fixation of CO2 under mild conditions.

A "two-in-one" dual activation strategy has been developed to give high-density hydrogen-bonding (HB) active units and Lewis acid (LA) active centres by immobilizing squaramides into metal-organic cages (MOCs). The obtained MOC served as an efficient catalyst for the chemical fixation of CO2 under mild conditions up to 99% yields with good recyclability, and the mechanism of high catalytic activity has been further explored.

Encapsulation of a metal-organic cage-based porous salt in silica nanopores.

A metal-organic cage (MOC)-based porous salt composed of cationic Zr-MOC and anionic Cu-MOC was incorporated into SBA-15 nanopores via a two-step impregnation method for the first time. The encapsulated MOC-based porous salt showed improved iodine adsorption capacity when compared with the bulk sample.

Creation of single molecular conjugates of metal-organic cages and DNA.

Here we report the development of an equimolar conjugate of a metal-organic cage (MOC) and DNA (MOC-DNA). Several MOC-DNA conjugates were assembled into a programmed structure by coordinating with a template DNA having a complementary base sequence. Moreover, conjugation with the MOC drastically enhanced the permeability of DNA through the lipid bilayer, presenting great potential as a drug delivery system.

Visualization of domain structure and piezoelectric energy harvesting in a ferroelectric metal-ligand cage.

The ferroelectric behaviour of an octahedral cage [[Ni6(H2O)12(TPTA)8]·(NO3)12·36H2O] (1) exhibiting high remnant polarization of 25.31 μC cm-2 is discovered. For the first time, clear domain structures and the characteristic electromechanical responses are demonstrated using piezoresponsive force microscopy for a thin film of 1. Owing to its mechanical energy conversion capability, polymer composites of 1 were employed as efficient piezoelectric nanogenerators.

Target-specific isolation of light-switchable metal–organic cages within metal–organic frameworks for tunable CO2 adsorption

Isolation of light-switchable metal–organic cages within the targeted cavities of metal–organic frameworks through light-assisted precise size control, thus providing an efficient, light-switchable adsorbent for tunable CO2 adsorption.

From an aluminum oxo cluster to an aluminum oxo cluster organic cage.

Presented herein is an example of the conversion of an aluminum oxo cluster (AlOC) to an aluminum oxo cluster organic cage (AlOCOC). We successfully synthesized the first example of an aluminum cluster-based organic cage-Al12 tetrahedral cage via an Al3 cluster. The use of 4-pyrazolecarboxylic acid plays an important role in the construction of the organic cage. Due to the presence of partially deprotonated ligands, the hydrogen-bonding interactions between the discrete tetrahedra generate porous supramolecular structures. Considering the high porosity and the abundant N-H sites, we further investigated the performance of the material towards iodine capture.

Chiral metal-organic cages decorated with binaphthalene moieties.

The construction of chiral nanoobjects with atomically precise nanostructures has attracted much more attention in the past decades. However, this field is still in its early stages. We designed and synthesized a series of chiral ligands containing the binaphthalene moiety and isophthalate module. Then, four chiral metal-organic cages (MOCs) were obtained through the coordination between isophthalate modules and copper ions. These chiral MOCs exhibit discrete, uniform and stable structures, good solubility and photoluminescence behaviors.

Metal–Organic Cage Extended Amorphous Network via Anionic Organic Linkers for Cr2O72– and Iodine Adsorption on Nanopores

The covalent linking of metal–organic cages (MOCs) with a nanoscale cavity is an efficient strategy to construct functional materials with different properties compared with bulk MOCs, but studies based on this topic are still less explored. In addition, toxic chemical and pollutant uptake, especially iodine vapor adsorption on MOC-based materials, still lacks investigation. Herein, an MOC-extended amorphous network (denoted MOC–DASD) via the covalent linking of an aldehyde-functionalized cationic Pd12L24 MOC (with about 3.5 nm in diameter) with an anionic organic linker, 4,4′-diamino-2,2′-stilbenedisulfonic acid (DASD), was constructed and applied to absorb Cr2O72– in water and capture I2 molecules in vapor. The covalent linkage of MOC and DASD via C═N bonds was confirmed by IR, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and ζ-potential tests. In addition, the original NO3– anions can be easily removed from the MOC–DASD due to the introduction of an anionic linker, thus releasing more effective cavities for guest adsorption. Although there is a lack of exchangeable anions, MOC–DASD still exhibits the ability to capture Cr2O72– in water with moderate capacity and high selectivity. In addition, the MOC–DASD showed a significantly enhanced iodine vapor uptake capacity. The iodine uptake capacity of MOC–DASD reached 3.67 g/g, which is 1.8 times higher than that of bulk MOC. A mechanistic study shows that some of the iodine was closely adsorbed by charge transfer. The release of iodine at 120 °C reveals that approximately 74% of the absorbed iodine can be removed, and the MOC can uptake the iodine again with a capacity of 1.5 g/g, showing good reusability.

Enantioselective fullerene functionalization through stereochemical information transfer from a self-assembled cage.

The regioselective functionalization of C60 remains challenging, while the enantioselective functionalization of C60 is difficult to explore due to the need for complex chiral tethers or arduous chromatography. Metal-organic cages have served as masks to effect the regioselective functionalization of C60. However, it is difficult to control the stereochemistry of the resulting fullerene adducts through this method. Here we report a means of defining up to six stereocentres on C60, achieving enantioselective fullerene functionalization. This method involves the use of a metal-organic cage built from a chiral formylpyridine. Fullerenes hosted within the cavity of the cage can be converted into a series of C60 adducts through chemo-, regio- and stereo-selective Diels-Alder reactions with the edges of the cage. The chiral formylpyridine ultimately dictates the stereochemistry of these chiral fullerene adducts without being incorporated into them. Such chiral fullerene adducts may become useful in devices requiring circularly polarized light manipulation.

Synthesis of a Tetrahedral Metal-Organic Supramolecular Cage with Dendritic Carbazole Arms.

In recent years, incredible endeavors have been devoted to the design and self-assembly of discrete metal-organic cages (MOCs) with expanding intricacy and functionality. The controlled synthesis of metal-organic supramolecular cages with large branched chains remains an interesting and challenging work in supramolecular chemistry. Herein, a tetrahedral metal-organic supramolecular cage (ZnII4L4) containing 12 dendritic carbazole arms is unprecedentedly constructed through coordination-driven subcomponent self-assembly and characterized in different ways. Interestingly, tetrahedral supramolecular Cage-1 exhibited the potential for aggregation-induced emission (AIE) performance and stimulus-responsive luminescence features, and it achieved color-tunable photoluminescence due to the introduction of dendritic carbazole arms. Crucially, owing to the great photophysical properties of Cage-1 in solution, Cage-1 was enabled to act as a fluorescent ink for the vapor-responsive recording and wiping of information.

Anion-Driven Programmable Chiral Self-Sorting in Metal-Organic Cages and Structural Transformations between Heterochiral and Homochiral Cages.

When a racemic mixture of chiral building blocks self-assembles to form discrete molecular or supramolecular cages, the system can adopt either social or narcissistic chiral self-sorting. However, control over such chiral self-sorting is hard to achieve with a desired choice of outcome. Herein, we report anion templated high-fidelity chiral self-sorting during the coordination-driven self-assembly of [Pd2 L4 ] metal-organic cages, with a racemic mixture of an axially chiral ligand. Upon varying the counter-anions, the outcome of the choice of chiral self-sorting, whether social or narcissistic, leading to kinetically favored heterochiral or thermodynamically favored homochiral cages, can be controlled through specific anion encapsulation. Non-encapsulating anion afforded a mixture of all possible diastereomers. Anion exchange enabled structural transformations between the diastereomers and the conversion of the mixture of diastereomers into homochiral diastereomers.

Host Spin-Crossover Thermodynamics Indicate Guest Fit.

Spin-crossover (SCO) metal-organic cages capable of switching between high-spin and low-spin states have the potential to be used as magnetic sensors and switches. Variation of the donor strength of heterocyclic aldehyde subcomponents in imine-based ligands can tune the ligand field for a FeII center, which results in both homoleptic and heteroleptic cages with diverse SCO behaviors. The tetrahedral SCO cage built from 1-methyl-1H-imidazole-2-carbaldehyde is capable of encapsulating various guests, which stabilize different cage spin states depending on guest size. Conversely, the SCO tetrahedron exhibits different affinities for guests in different spin states, which is inferred to result from subtle structural differences of the cavity caused by the change in metal center spin state. Examination of SCO thermodynamics across a series of host-guest complexes enabled sensitive probing of guest fit to the host cavity, providing information complementary to binding-constant determination.

Cluster-Based Crystalline Materials for Iodine Capture.

The treatment of radioactive iodine in nuclear waste has always been a critical issue of social concern. The rational design of targeted and efficient capture materials is of great significance to the sustainable development of the ecological environment. In recent decades, crystalline materials have served as a molecular platform to study the binding process and capture mechanism of iodine molecules, enabling people to understand the interaction between radioactive iodine guests and pores intuitively. Cluster-based crystalline materials, including molecular clusters and cluster-based metal-organic frameworks, are emerging candidates for iodine capture due to their aggregative binding sites, precise structural information, tunable pores/packing patterns, and abundant modifications. Herein, recent progress of different types of cluster materials and cluster-dominated metal-organic porous materials for iodine capture is reviewed. Research prospects, design strategies to improve the affinity for iodine and possible capture mechanisms are discussed.

Complementarity and Preorganisation in the Assembly of Heterometallic–Organic Cages via the Metalloligand Approach—Recent Advances

The design of new metallocage polyhedra towards pre-determined structures can offer both practical as well as intellectual challenges. In this mini-review we discuss a selection of recent examples in which the use of the metalloligand approach has been employed to overcome such challenges. An attractive feature of this approach is its stepwise nature that lends itself to the design and rational synthesis of heterometallic metal–organic cages, with the latter often associated with enhanced functionality.