Twisted-Planar Molecular Engineering with Sonication-Induced J-Aggregation To Design Near-Infrared J-Aggregates for Enhanced Phototherapy.

J-aggregates show great promise in phototherapy, but are limited to specific molecular skeletons and poor molecular self-assembly controllability. Herein, we report a twisted-planar molecular strategy with sonication-induced J-aggregation to develop donor-acceptor (D-A) type J-aggregates for phototherapy. With propeller aggregation-induced emission (AIE) moieties as the twisted subunits and thiophene as the planar π-bridge, the optimal twisted-planar π-interaction in MTSIC induces appropriate slip angle and J-aggregates formation, redshifting the absorption from 624 nm to 790 nm.

Dynamic Rare-Earth Metal-Organic Frameworks Based on Molecular Rotor Linkers with Efficient Emissions and Ultrasensitive Optical Sensing Performance.

4,4',4″-Triphenylamine tricarboxylate (TPA-COOH) with a distinct molecular rotor structure was reacted with rare-earth (RE) metal ions to obtain seven dynamic RE-based luminescent MOFs () (i.e., emission colors in the blue, yellow-green, red, and near-infrared regions and emission peak wavelengths between 400 and 1600 nm) via the effective transfer of absorbed energy from TPA-COOH to the RE metal ions through the antenna effect.

Hourglass-shaped europium cluster-based secondary building unit in metal-organic framework for photocatalytic wastewater purification and sterilization via enhanced reactive oxygen species production.

A large number of diseases caused by water pollution have become a global public health issue, and the development and construction of innovative and efficient photocatalytic systems for water remediation is vital to improve water quality and prevent bacteria-induced diseases. Herein, a europium-based metal-organic framework (Eu-MOF) was self-assembled with complex hourglass-shaped Eu clusters as secondary building units (SBUs), achieving excellent photoinduced reactive oxygen species (ROS) generation ability. Moreover, Eu-MOF can quickly and efficiently degrade organic dyes and kill a variety of bacteria under low-power light irradiation conditions.

One-Pot In Situ Construction of a Highly Stable Acylhydrazone-Derived Dy Cluster with Photodynamic Sterilization Property.

The extremely low stability of lanthanide clusters with precise structures and nanometer dimensions in aqueous solutions limits their application in the field of photodynamic sterilization. In this study, an hourglass-shaped nine-nucleated Dy cluster () with excellent light-driven reactive oxygen species (ROS) generation ability and photodynamic sterilization property was constructed using acylhydrazone multidentate chelating ligands obtained via an in situ reaction. The eight chelating ligands were distributed outside cluster , tightly wrapping the cluster core, thus preventing solvent molecules from attacking the cluster nucleus and ensuring the stability of cluster in solution, which was demonstrated via X-ray diffraction and high-resolution electrospray ionization mass spectrometry (HRESI-MS).

Aggregation induced emission dynamic chiral europium(III) complexes with excellent circularly polarized luminescence and smart sensors.

The synthesis of dynamic chiral lanthanide complex emitters has always been difficult. Herein, we report three pairs of dynamic chiral Eu complex emitters (R/S-Eu-R-1, R = Et/Me; R/S-Eu-Et-2) with aggregation-induced emission. In the molecular state, these Eu complexes have almost no obvious emission, while in the aggregate state, they greatly enhance the Eu emission through restriction of intramolecular rotation and restriction of intramolecular vibration.

Different anion (NO and OAc)-controlled construction of dysprosium clusters with different shapes.

The complex hydrolysis process and strong uncertainty of self-assembly rules have led to the precise synthesis of lanthanide clusters still being in the "blind-box" stage and simplifying the self-assembly process and developing reliable regulation strategies have attracted widespread attention. Herein, different anions are used to induce the construction of a series of dysprosium clusters with different shapes and connections. When the selected anion is NO, it blocks the coordination of metal sites around the cluster through the terminal group coordination mode, thereby controlling the growth of the cluster.

Coordination recognition of differential template units of lanthanide chiral chain.

Coordination-driven self-assembly processes often produce remarkable structures. In particular, self-assembly processes mediated by chiral template units have provided research ideas for analyzing the formation of chiral macromolecules in living organisms. In this study, by regulating the proportion of reaction raw materials in the "one-pot" synthesis of lanthanide complexes, we constructed chiral template units with different coordination orientations.

Aggregation-Induced Emission via the Restriction of the Intramolecular Vibration Mechanism of Pinacol Lanthanide Complexes.

Pinacol lanthanide complexes (Ln = Dy and Tb) with the restriction of intramolecular vibration were obtained for the first time via an in situ solvothermal coordination-catalyzed tandem reaction using cheap and simple starting materials, thereby avoiding complex, time-consuming, and expensive conventional organic synthesis strategies. A high-resolution electrospray ionization mass spectrometry (HRESI-MS) analysis confirmed the stability of in an organic solution. The formation process of was monitored in detail using time-dependent HRESI-MS, which allowed for proposing a mechanism for the formation of pinacol complexes via in situ tandem reactions under one-pot coordination-catalyzed conditions.

A biocompatible pure organic porous nanocage for enhanced photodynamic therapy.

Porphyrin-based photosensitizers have been widely utilized in photodynamic therapy (PDT), but they suffer from deteriorating fluorescence and reactive oxygen species (ROS) due to their close π-π stacking. Herein, a biocompatible pure organic porphyrin nanocage (Py-Cage) with enhanced both type I and type II ROS generation is reported for PDT. The porphyrin skeleton within the Py-Cage is spatially separated by four biphenyls to avoid the close π-π stacking within the nanocage.

Pure Organic AIE Nanoscintillator for X-ray Mediated Type I and Type II Photodynamic Therapy.

X-ray induced photodynamic therapy (X-PDT) circumvents the poor penetration depth of conventional PDT with minimal radio-resistance generation. However, conventional X-PDT typically requires inorganic scintillators as energy transducers to excite neighboring photosensitizers (PSs) to generate reactive oxygen species (ROS). Herein, a pure organic aggregation-induced emission (AIE) nanoscintillator (TBDCR NPs) that can massively generate both type I and type II ROS under direct X-ray irradiation is reported for hypoxia-tolerant X-PDT.

"One-Pot" In Situ Tandem Reaction─Dy(III) Coordination-Catalyzed Multicomponent Condensation of Salicylaldehyde Derivatives to Obtain Ketals.

It is difficult to subject simple reaction starting materials to a "one-pot" in situ tandem reaction without post-treatment under mild reaction conditions to obtain multimers with complex structural linkages. In organic synthesis, acetal reactions are often used to protect derivatives containing carbonyl functional groups. Therefore, acetal products tend to have very low stability, and performing multi-step condensation to obtain complex multimeric products is difficult.

Manipulating Solvothermal Coordination-Catalyzed Tandem Reactions to Construct Dysprosium-Based Complexes with Different Shapes and Zero-Field SMM Behaviors.

By changing the coordination anions (OAc and Cl), reaction temperature, solvent, and ligand substituents, four Dy(III)-based complexes were obtained by directed synthesis, which are [Dy(L)(L)(OAc)]·4CHOH·3HO (, L = 1,3,4-thiadiazole-2,5-diamine, HL = 6,6'-(((1,3,4-thiadiazole-2,5-diyl)bis(azanediyl))bis(((3-ethoxy-2-hydroxybenzyl)oxy)methylene))bis(2-ethoxyphen), [Dy(L)(OAc)]·CHOH·HO (, HL = 2-(((5-amino-1,3,4-thiadiazol-2-yl)amino)((3-ethoxy-2-hydroxybenzyl)oxy)methyl)-6-ethoxyphenol)), [Dy(L)(L)(μ-OH)(CHO)Cl]Cl (, HL = 2-hydroxy-3-methoxybenzaldehyde, HL = 2-(((5-amino-1,3,4-thiadiazol-2-yl)amino)(hydroxy)methyl)-6-methoxyphenol), and [Dy(L)(L)(μ-OH)(CHO)Cl]Cl·2HO (, HL = 2-hydroxy-3-ethoxybenzaldehyde, HL = 2-(((5-amino-1,3,4-thiadiazol-2-yl)amino)(hydroxy)methyl)-6-ethoxyphenol). A series of acetal products (HL, HL, HL, and HL) were obtained through dehydration tandem reactions. Magnetic studies show that complexes - exhibited different single-molecule magnet behavior under zero-field conditions.

Anion-Manipulated Hydrolysis Process Assembles of Giant High-Nucleation Lanthanide-Oxo Cluster.

Widespread concern has been raised over the synthesis of highly nucleated lanthanide clusters with special shapes and/or specific linkages. Construction of lanthanide clusters with specific shapes and/or linkages can be achieved by carefully regulating the hydrolysis of lanthanide metal ions and the resulting hydrolysis products. However, studies on the manipulation of lanthanide-ion hydrolysis to obtain giant lanthanide-oxo clusters have been few.

Assembly of pinwheel/twist-shaped chiral lanthanide clusters with rotor structures by an annular/linear growth mechanism and their magnetic properties.

Although progress has been made in the design and synthesis of chiral lanthanide clusters with pleasing structural connections and special shapes, assembly rules that guide their directional construction are still lacking. We reacted R/S-mandelic acid hydrazide, 2,3-dihydroxybenzaldehyde and DyCl·6HO under solvothermal conditions to obtain two octanuclear chirality clusters R-1 and S-1, which are the enantiomers of each other. R/S-mandelic acid hydrazide and 2,3-dihydroxybenzaldehyde underwent an reaction under "one-pot" conditions to generate a monohydrazone-type organic ligand R/S-mandelic acid hydrazide-2,3-dihydroxybenzaldehyde hydrazone (R/S-HL).

Alkali metal-linked triangular building blocks assemble a high-nucleation lanthanoid cluster based on single-molecule magnets.

The metallic central magnetic axes in high-nucleation clusters with complex structural connections tend to be disorganized and cancel each other out. Therefore, high-nucleation clusters cannot easily exhibit single-molecule magnets (SMMs) behaviors. Herein, we select a triple-core building block (DyK, ) and use linked diamagnetic alkali metal to form an open, spherical, high-nucleation cluster DyNa () with SMM behavior.

Giant Crown-Shaped Dy Nanocluster with High Acid-Base Stability Assembled by an out-to-in Growth Mechanism.

Lanthanoid metal ions have large ionic radii, complex coordination modes, and easy distortion of coordination spheres, but the design and synthesis of high-nucleation lanthanoid clusters with high stability in solution (especially aqueous solution) are challenging. Herein, a diacylhydrazone ligand (HL) with multidentate chelating coordination sites was used to react with Dy(OAc)·4HO under solvothermal conditions to obtain an example of a 34-nucleus crown-shaped dysprosium cluster [Dy(L)(μ-OH)(μ-OH)(μ-O)(OAc)(OCH)(HO)](OAc) (). Structural analysis showed that the bisacylhydrazone ligand HL with polydentate chelate coordination sites could rapidly capture Dy ions, thereby forming 34-nucleus crown-shaped dysprosium cluster following the out-to-in growth mechanism.

Smart Tetraphenylethene-Based Luminescent Metal-Organic Frameworks with Amide-Assisted Thermofluorochromics and Piezofluorochromics.

Luminescent metal-organic frameworks (MOFs) are appealing for the design of smart responsive materials, whereas aggregation-induced emission (AIE) fluorophores with twisted molecular rotor structure provide exciting opportunities to construct MOFs with new topology and responsiveness. Herein, it is reported that elongating AIE rotor ligands can render the newly formed AIE MOF (ZnETTB) (ETTB = 4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-3,5-dicarboxylic acid))) with more elasticity, more control for intramolecular motion, and specific amide-sensing capability. ZnETTB shows specific host-guest interaction with amide, where N,N-diethylformamide (DEF), as an example, is anchored through CH···O and CH···π bonds with Zn cluster and ETTB ligand, respectively.

Series of the Largest Dish-Shaped Dysprosium Nanoclusters Formed by Reactions.

A three-dimensional supermolecule structure is easily formed due to the diverse coordination modes of high-oxidation-state lanthanide metal ions. However, the design and construction of zero-dimensional (0 D) dish-shaped high-nuclearity lanthanide clusters are difficult. Herein, for the first time, we synthesized a series of the largest dish-shaped high-nuclearity lanthanide nanoclusters (-) by tandem reactions under solvothermal one-pot conditions.

Porphyrin-Based Two-Dimensional Layered Metal-Organic Framework with Sono-/Photocatalytic Activity for Water Decontamination.

Water treatment is crucial to improve the water quality and reduce diarrheal and chronological diseases caused by excessive discharge of organic dyes and other waste. The development and expansion of efficient catalysts for the degradation and sterilization of organic dyes has attracted widespread attention. Herein, we report an example of a porphyrin-based two-dimensional layered metal-organic framework (MOF) (2DZnTcpp) and its efficient sono-/photocatalytic degradation of organic dyes and bactericidal activity.

Truncation reaction regulates the out-to-in growth mechanism to decrypt the formation of brucite-like dysprosium clusters.

Specially shaped high-nuclear lanthanide cluster assembly has attracted widespread attention, but the study of their self-assembly mechanism is still stagnant. Herein, we used a polydentate chelating bis-acylhydrazone ligand to construct a rare 16-nuclear dysprosium cluster 1 with a brucite-like structure. The capture agents, pivalic acid and di(pyridin-2-yl)methanone, were added into the reaction system, and the hexanuclear dysprosium cluster 2 and heptanuclear dysprosium cluster 3 were obtained, respectively.

A Series of High-Nuclear Gadolinium Cluster Aggregates with a Magnetocaloric Effect Constructed through Two-Component Manipulation.

The serialized expansion of high-nuclear clusters usually includes the controlled variable method and changes only a single variable. However, changing both variables will greatly increase the complexity of the reaction simultaneously. Therefore, the use of a two-component regulation reaction is rare.

Two Decanuclear DyCo ( = 2, 4) Nanoclusters: Structure, Assembly Mechanism, and Magnetic Properties.

The aggregation and formation of heterometallic nanoclusters usually involves a variety of complex self-assembly processes; thus, the exploration of their assembly mechanisms through process tracking is more challenging than that for homometallic nanoclusters. We explored here the effect of solvent on the formation of heterometallic clusters, which gave two heterometallic nanoclusters, [DyCo(μ-OCH)(L)(HL)(OAc)(NO)(CHCN)]·CHCN·HO () and [DyCo(L)(HL)(OAc)(OCHCHOH)(HOCHCHOH)(HO)]·9CHCN (), with the HL ligand formed from the in situ condensation reaction of 3-amino-1,2-propanediol with 2-hydroxy-1-naphthaldehyde in the presence of Co(OAc)·4HO and Dy(NO)·6HO. It is worth noting that the skeleton of cluster has a high stability under high-resolution electrospray ionization mass spectrometry (HRESI-MS) conditions with a gradually increasing energy of the ion source.

Multifunctional Binuclear Ln(III) Complexes Obtained via Tandem Reactions: Multiple Photoresponses to Volatile Organic Solvents and Anticounterfeiting and Magnetic Properties.

The design and synthesis of simple lanthanide complexes with multiple functions have been widely studied and have faced certain challenges. Herein, we successfully synthesized the series of binuclear lanthanide complexes [Ln()(NO)] (H = 2-amino-1,2-bis(pyridin-2-yl)ethanol; Ln = Dy (), Tb (), Ho () Er ()) via the self-condensation of Ln(NO)·6HO-catalyzed 2-aminomethylpyridine (16 steps) under solvothermal conditions. was mixed with different volatile organic solvents, and photoluminescence tests demonstrated that it showed an excellent selective photoresponse to chloroform (CHCl).

Substitution Effects Regulate the Formation of Butterfly-Shaped Tetranuclear Dy(III) Cluster and Dy-Based Hydrogen-Bonded Helix Frameworks: Structure and Magnetic Properties.

The generation of two types of complexes with different topological connections and completely different structural types merely via the substitution effect is extremely rare, especially for -CH and -CH substituents with similar physical and chemical properties. Herein, we used 3-methoxysalicylaldehyde, 1,2-cyclohexanediamine, and Dy(NO)·6HO to react under solvothermal conditions (CHOH:CHCN = 1:1) at 80 °C to obtain the butterfly-shaped tetranuclear Dy cluster [Dy()(μ-O)(NO)] (, H = 6,6'-((1,1')-(cyclohexane-1,3-diylbis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol)). The ligand H was obtained by the Schiff base reaction of 3-methoxysalicylaldehyde and 1,2-cyclohexanediamine.