Giant Expanded Porous Metallo-Hexagons.

Molecular self-assembly is a widely recognized approach for fabricating biomimetic functional nanostructures. Here, we report the synthesis of two giant hollow coronoid-like supramolecular hexagons, H1 and H2. These hexagons feature large cavities, showcasing unique inner and outer hexagons fixed by specific connectivities for enhanced stability and high metal center density. H1 exhibits properties that can be transformed through the thermodynamic conversion of the metallopolymer formed by L1 and L2. With an edge length of 6.8 nm, H2 is one of the largest hexagons reported to date. 1D and 2D NMR, TEM, ESI-MS, and TWIM-MS experiments provided conclusive evidence for the composition and structure of the assembled hexagons. This work demonstrates the feasibility of constructing giant supramolecular architectures with precise control over their size and shape, opening up new possibilities for the design and synthesis of sophisticated supramolecules and nonbiological materials.

Segmented Template-Directed Self-Assembly of Giant Truncated Triangular Supramolecules.

The template-directed strategy has been extensively employed for the construction of supramolecular architectures. However, with the increase in the size and complexity of these structures, the synthesis difficulty of the templates escalates exponentially, thereby impeding the widespread application of this strategy. In this study, two truncated triangles T1 and T2 were successfully self-assembled through a novel segmented template strategy by segmenting the core triangular template into portions. Two metallo-organic ligands L2 and L3 were designed and synthesized by dividing the central stable triangle into three separate parts and incorporating them into the precursor ligands, which served as templates to guide the self-assembly process with ligands L1 and L4, respectively. The assembled structures were unambiguously characterized by multidimensional and multinuclear NMR (1H, COSY, NOESY), multidimensional mass spectrometry analysis (ESI-MS and TWIM-MS), and transmission electron microscopy (TEM). Moreover, we observed the formation of fiberlike nanotubes from single-molecule triangles by hierarchical self-assembly.

Adjusting the Architecture of Heptagonal Metallo-Macrocycles by Embedding Metal Nodes into the Backbone.

Coordination-driven self-assembly has been extensively employed for the bottom-up construction of discrete metallo-macrocycles. However, the prevalent use of benzene rings as the backbone limits the formation of large metallo-macrocycles with more than six edges. Herein, by embedding metal nodes into the ligand backbone, we successfully regulated the ligand arm angle and assembled two giant heptagonal metallo-macrocycles with precise control. The angle between two arms at position 4 of the central terpyridine (tpy) extended after complexation with metal ions, leading to ring expansion of the metallo-macrocycle. The assembled structures were straightforwardly identified through multi-dimensional NMR spectroscopy (1 H, COSY, NOESY), multidimensional mass spectrometry analysis (ESI-MS and TWIM-MS), transmission electron microscopy (TEM), as well as scanning tunneling microscopy (STM). In addition, the catalytic performances of metallo-macrocycles in the oxidation of thioanisole were studied, with both supramolecules exhibiting good conversion rates. Furthermore, fiber-like nanostructures were observed from single-molecule heptagons by hierarchical self-assembly.

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.

Crystalline Metallo-Organic Cage by Triphenylene-Cored Hexaterpyridine for Fast Iodine Capture.

In recent years, radioactive iodine capture has played an important role in nuclear waste treatment. However, most of the adsorbents possess low economic efficiency and undesirable reutilization in practical application. In this work, a terpyridine-based porous metallo-organic cage was assembled for iodine adsorption. Through synchrotron X-ray analysis, the metallo-cage was found to have a porous hierarchical packing mode with inherent cavity and packing channel. By taking advantage of polycyclic aromatic units and charged ⟨tpy-Zn2+-tpy⟩ (tpy = terpyridine) coordination sites in the structure, this nanocage exhibits an excellent ability to capture iodine in both the gas phase and aqueous medium, and the crystal state of the nanocage shows an ultrafast kinetic process of capturing I2 in aqueous solution within 5 min. The calculated maximum sorption capacities for I2 based on the Langmuir isotherm models are 1731 and 1487 mg g-1 for amorphous and crystalline nanocages, which is noticeably higher than most of the reported iodine sorbent materials in the aqueous phase. This work not only provides a rare example of iodine adsorption by a terpyridyl-based porous cage but also expands the applications of terpyridine coordination systems into iodine capture.

Multi-functionalized Metallo-Supramolecular Spoked Wheels: Their Emission-Tunable Hierarchically Assembled System with Dye Molecules.

Supramolecular architectures with multiple emissive units are especially appealing due to their desired properties, such as artificial light harvesting and white-light emission. But fully achieving multi-wavelength photoluminescence in a single supramolecular architecture remains a challenge. In this paper, functionalized supramolecular architectures containing twelve metal centers and six pyrene moieties were nearly quantitatively synthesized by multi-component self-assembly and fully characterized by 1D and 2D nuclear magnetic resonance, dynamic light scattering, electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy. Moreover, the hierarchical nano-assemblies were prepared by introducing anionic dyes to the positively charged self-assembled framework, which contained three luminescence centers, namely, pyrene, tpy-Cd coordination parts, and Sulforhodamine B anions. Such a hierarchically assembled system displayed tunable emission by taking full advantage of aggregation-induced emission enhancement, aggregation-caused quenching, and fluorescence resonance energy transfer effects and showed the diverse emission colors. This research provides a new insight for constructing multiple emissive metallo-supramolecular assemblies.

Heteroleptic/Heterometallic Sierpinski Triangle with Room Temperature Fluorescence Emission and Photocatalytic Amine Oxidation Activity.

As a result of their optical and redox properties, bipyridyl (bpy) and terpyridyl (tpy) ruthenium complexes play vital roles in numerous domains. Herein, the design and synthesis of two bipyridyl and terpyridyl ruthenium(II) building units L1 and L2 are explained. A [Ru(bpy)3]2+ functionalized triangle S1 and a Sierpinski triangle S2 were synthesized in almost quantitative yields by the self-assembly of L1 with Zn2+ ions and by the heteroleptic self-assembly of L1 and L2 with Zn2+ ions, respectively. The Sierpinski triangle S2 contains the coordination metals [Ru(bpy)3]2+, [Ru(tpy)2]2+, and [Zn(tpy)2]2+. According to research on the catalytic activity of amine oxidation on supramolecules S1 and S2, the benzylamine substrates were nearly entirely transformed to N-benzylidenebenzylamine derivatives after 1 h under a Xe lamp. Furthermore, the observed ruthenium-containing terpyridyl supramolecule S2 maintains high luminous performance at ambient temperature. This discovery opens up new possibilities for the rational molecular design of terpyridyl ruthenium fluorescent materials and catalytic functional materials.

The Photothermal Conversion and UV Resistance of Silk Fabrics Being Achieved through Surface Modification with C@SiO2 Nanoparticles.

With the improvement in people's living standards, the development and application of smart textiles are receiving increasing attention. In this study, a carbon nanosurface was successfully coated with a SiO2 layer to form C@SiO2 nanomaterials, which improved the dispersion of carbon nanomaterials in an aqueous solution and enhanced the absorption of light by the carbon nanoparticles. C@SiO2 nanoparticles were coupled on the surface of silk fabric with the silane coupling agent KH570 to form C@SiO2 nanosilk fabric. The silk fabric that was subjected to such surface modification was endowed with a special photothermal function. The results obtained with scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and infrared spectroscopy (FTIR) showed that C@SiO2 nanoparticles were successfully modified on the surface of the silk fabric. In addition, under the irradiation of near-infrared light with a power of 20 W and a wavelength of 808 nm, the C@SiO2 nanosilk fabric experienced rapid warming from 23 °C to 60 °C within 30 s. After subjecting the functional fabric to hundreds of photothermal experiments and multiple washes, the photothermal efficiency remained largely unchanged and proved to be durable and stable. In addition, the thermogravimetric (TG) analysis results showed that the C@SiO2 nanoparticles contributed to the thermal stability of the silk fabric. The UV transmittance results indicated that C@SiO2 nanofabric is UV-resistant. The silk modification method developed in this study is low-cost, efficient, and environmentally friendly. It has some prospects for future applications in the textile industry.

The Marriage of Sierpinski Triangles and Platonic Polyhedra.

Fractal structures with self-similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry-directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpinski tetrahedron ST-T and the Sierpinski octahedron ST-O, in which each possesses a fractal Sierpinski triangle on their independent faces. These two discrete complexes are formed in near-quantitative yield from the multi-component self-assembly of truncated Sierpinski triangular kernel L1 with tribenzotriquinacene-based hexatopic and anthracene-based tetratopic terpyridine ligands (L3 and L4 ) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2 ). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules.

Heterometallic Polyoxotitanium Clusters as Bifunctional Electrocatalysts for Overall Water Splitting.

Incorporating heterometal into titanium-oxygen clusters (TOCs) is an effective way to improve its catalytic activity. Herein, we synthesize three novel heterometallic TOCs with the formula of [Ti6Cu2O7(Dmg)2(OAc)4(iPrO)6][H2Ti6Cu2O7(Dmg)2(OAc)4(iPrO)8] ({Ti6Cu2}), [Ti8Cu2O9(Dmg)2(OAc)2(iPrO)12] ({Ti8Cu2}), and [Ti10Co2O6(Dmg)2(Pdc)4(iPrO)18Cl3] ({Ti10Co2}, DmgH2 = dimethylglyoxime; PdcH2 = pyridine-2,3-dicarboxylic acid) using dimethylglyoxime and different carboxylates as the synergistic ligands. By depositing the clusters {Ti6Cu2} and {Ti10Co2} on carbon cloth as electrodes, we investigated the electrocatalytic performance of TOCs for full water splitting for the first time. To reach a 10 mA cm-2 current density in an alkaline solution, the {Ti10Co2}@CC electrode needs an overpotential as low as 120 and 400 mV for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), respectively. In addition, full water-splitting equipment with {Ti10Co2}@CC as a cathode and an anode need only 1.67 V to deliver a current density of 10 mA cm-2. Our work confirmed the potential of noble metal-free TOCs as bifunctional cluster-based electrocatalysts for water splitting, and their activities can be tuned by doping with different metal ions.

Tetratopic Terpyridine Building Unit as a Precursor to Wheel-Like Metallo-Supramolecules.

In an effort to construct molecules with distinct shapes and functions, the design and synthesis of multitopic ligands are often able to play an important role. Here, we report the synthesis of a novel tetratopic organic ligand LA, which can be viewed as a bis-tenon with successive angular orientations in space. The particular ligand has been treated with different tailored metal-organic ligands to afford new members of the molecular wheel family (multi-rhomboidal-shaped wheel and bis-trapezium-shaped wheel) that show enhanced stability. Two-dimensional (2D) diffusion nuclear magnetic resonance (NMR) spectroscopy (DOSY), electrospray ionization (ESI) mass spectrometry, traveling wave ion mobility (TWIM), and gradient tandem mass spectrometry (gMS2) experiments, as well as molecular modeling, have been employed to provide structural information and differentiate the isomeric separation process. In addition, considering that LA has rotational properties, it is expected to open the door to functional supramolecules and stimuli-responsive materials.

Modular Construction of a Tessellated Octahedron, its Hierarchical Spherical Aggregate Behavior, and Electrocatalytic CO2 Reduction Activity.

Coordination-driven self-assembly has led to the formation of various aesthetical polyhedrons and compounds with advanced functions. Whereas two-dimensional supramolecules with complex and giant skeletons are plentiful, the constructions of polyhedrons are limited by using basic polygons as the panels. Herein, we report the modular synthesis of a tessellated triangle and tessellated octahedron with metal-organic modules as the panels and formed via template-driven self-assembly. These architectures have diameters on the order of 10.9 nm and molecular weights greater than 84 kDa. Interestingly, fiber and spherical-like nanostructures could be formed from the tessellated triangles and octahedrons, respectively, through hierarchical self-assembly. In addition, after hybridization with carbon nanotubes, the supramolecules exhibit electrochemical reduction activity for CO2 to CO.

MOF Encapsulating N-Heterocyclic Carbene-Ligated Copper Single-Atom Site Catalyst towards Efficient Methane Electrosynthesis.

The exploitation of highly efficient carbon dioxide reduction (CO2 RR) electrocatalyst for methane (CH4 ) electrosynthesis has attracted great attention for the intermittent renewable electricity storage but remains challenging. Here, N-heterocyclic carbene (NHC)-ligated copper single atom site (Cu SAS) embedded in metal-organic framework is reported (2Bn-Cu@UiO-67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at -1.5 V vs. RHE with a current density of 420 mA cm-2 . The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s-1 . The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn-Cu, significantly increasing the availability of each catalytic center.

Russian-Doll-Like Molecular Cubes.

Nanosized cage-within-cage compounds represent a synergistic molecular self-assembling form of three-dimensional architecture that has received particular research focus. Building multilayered ultralarge cages to simulate complicated virus capsids is believed to be a tough synthetic challenge. Here, we synthesize two large double-shell supramolecular cages by facile self-assembly of presynthesized metal-organic hexatopic terpyridine ligands with metal ions. Differing from the mixture of prisms formed from the inner tritopic ligand, the redesigned metal-organic hexatopic ligands bearing high geometric constraints that led to the exclusive formation of discrete double-shell structures. These two unique nested cages are composed of inner cubes (5.1 nm) and outer huge truncated cubes (12.0 and 13.2 nm) with six large bowl-shape subcages distributed on six faces. The results with molecular weights of 75 232 and 77 667 Da were among the largest synthetic cage-in-cage supramolecules reported to date. The composition, size and shape were unambiguously characterized by a combination of 1H NMR, DOSY, ESI-MS, TWIM-MS, TEM, AFM, and SAXS. This work provides an interesting model for functional recognition, delivery, and detection of various guest molecules in the field of supramolecular materials.

Construction of Macromolecular Pinwheels Using Predesigned Metalloligands.

Developing a methodology to build target structures is one of the major themes of synthetic chemistry. However, it has proven to be immensely challenging to achieve multilevel elaborate molecular architectures in a predictable way. Herein, we describe the self-assembly of a series of pinwheel-shaped starlike supramolecules through three rationally preorganized metalloligands L1-L3. The key octa-uncomplexed terpyridine (tpy) metalloligand L3, synthesized with an 8-fold Suzuki coupling reaction to metal-containing complexes, has four different types of terpyridines connected with three ⟨tpy-Ru2+-tpy⟩ units, making this the most subunits known so far for a preorganized module. Based on the principle of geometric complementation and the high "density of coordination sites", these metalloligands were assembled with Zn2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields. With molecular weights ranging from 16756 to 56053 Da and diameters of 6.7-13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.

Reinforced Topological Nanoassemblies: 2D Hexagon-Fused Wheel to 3D Prismatic Metallo-Lamellar Structure with Molecular Weight of 119 K Daltons.

By a precise metallo-ligand design, the advanced coordination-driven self-assembly could succeed in the preparation of giant molecular weight of the metallo-architectures. However, the synthesis of a single discrete high-molecular-weight (>100 K Da) structure has not been demonstrated due to the insurmountable synthetic challenge. Herein, we present a two-dimensional wheel structure (W1) and a gigantic three-dimensional dodecagonal prism-like architecture (P1), which were generated by multicomponent self-assembly of two similar metallo-organic ligands and a core ligand with metal ions, respectively. The giant 2D-suprastructure W1 with six hexagonal metallacycles that fused to the central spoke wheel was first achieved in nearly quantitative yield, and then, directed by introducing a meta-substituted coordination site into the key ligand, the supercharged (36 Ru2+ and 48 Cd2+ ions) double-decker prismatic structure P1 with two wheel structure W1s serve as the surfaces and 12 connectivities serve as the edges, where a molecular weight up to 119 498.18 Da was accomplished. The expected molecular composition and size morphology was unequivocally characterized by nuclear magnetic resonance, mass spectrometry, and transmission electron microscopy investigations. The introduction of a wheel structure is able to add considerable stability and complexity to the final architecture. These well-defined scaffolds are expected to play an important role in the functional materials field, such as molecular encapsulation and medicine sustained release.

Giant Truncated Metallo-Tetrahedron with Unexpected Supramolecular Aggregation Induced Emission Enhancement.

The artificial synthesis of giant, three-dimensional, and shell-like architectures with growing complexity and novel functionalities is an especially challenging task for chemists. Fullerenes and self-assembled cages are remarkable examples that are proven milestones in the field of functional materials. Herein, we present another unique system: a giant terpyridine-based truncated metallo-tetrahedral architecture that includes densely-packed ionic pairs with a significant internal cavity. This huge metallo-tetrahedron with a molecular weight up to 70 000 Da was self-assembled simultaneously with 64 components: 12 large antler-shaped ligands (5), 4 star-shaped ligands (6), and 48 Cd2+ ions. Surprisingly, the giant tetrahedron shows broad visible emission (400-640 nm) and aggregation induced emission enhancement (AIEE) via a hierarchical assembly into highly-ordered nanoaggregates. A tunable emission color and near white-light emission in mixed solvent systems were also achieved. The present work not only affords an effective approach to the creation of giant shell-like architectures that can be used to mimic biological viruses and chemical frameworks but also provides a new class of functional metallo-architectures.

Abnormal perfusion fluctuation and perfusion connectivity in bipolar disorder measured by dynamic arterial spin labeling.

OBJECTIVES: We sought to evaluate whether dynamic Arterial Spin Labeling (dASL), a novel quantitative technique robust to artifacts and noise that especially arise in inferior brain regions, could characterize neural substrates of BD pathology and symptoms. METHODS: Forty-five subjects (19 BD patients, 26 controls) were imaged using a dASL sequence. Maps of average perfusion, perfusion fluctuation, and perfusion connectivity with anterior cingulate cortex (ACC) were derived. Patient symptoms were quantified along four symptom dimensions determined using factor analysis of the subjects from the Bipolar and Schizophrenia Network on Intermediate Phenotypes (BSNIP) study. Maps of the perfusion measures were compared between BD patients and controls and correlated with the symptom dimensions in the BD patients only by voxel-level and region-level analyses. RESULTS: BD patients exhibited (i) significantly increased perfusion fluctuations in the left fusiform and inferior temporal regions (P = .020, voxel-level corrected) and marginally increased perfusion fluctuations in the right temporal pole and inferior temporal regions (P = .063, cluster-level corrected), (ii) significantly increased perfusion connectivity between ACC and the occipitoparietal cortex (P = .050, cluster-level corrected). In BD patients, positive symptoms were negatively associated with ACC perfusion connectivity to the right orbitofrontal and superior frontal regions (P = .002, cluster-level corrected) and right orbitofrontal and inferior frontal regions (P = .023, cluster-level corrected). CONCLUSION: The abnormal perfusion fluctuations and connectivity alterations may underlie the mood fluctuations and cognitive and emotional dysregulation that characterize BD.

Tetraphenylethylene(TPE)-Containing Metal-Organic Nanobelt and Its Turn-on Fluorescence for Sulfide (S2-).

A metal-organic supramolecular nanobelt was synthesized by quantitative self-assembling terpyridine-functionized tetraphenylethylene (TPE) and Cd2+, which only showed a weak emission both in solution or aggregated state. Nevertheless, nanobelt complex could be transferred to a fluorescence turn-on sensor to S2- by taking advantage of the structural transformation from nanobelt to its fluorescent ligand.

Precise Self-Assembly of Molecular Four- and Six-Pointed Stars.

A novel metal-organic ligand (MOL 2) has been prepared by linking two V-shaped bis-terpyridines with one X-shaped tetrakis-terpyridine through the stable connectivity. The complexation between MOL 2, X-shaped tetrakis-terpyridine, and Zn2+ gave rise to a supramolecular C6-symmetrical six-pointed star quantitatively. In addition, a mixture of MOL 2, K-shaped tetrakis-terpyridine, and Zn2+ afforded a C2-symmetrical four-pointed star. These metallo-supramolecular architectures were adequately characterized by NMR, ESI-MS, TWIM-MS, and TEM analyses.