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).

New types of open-framework vanadium borophosphates with photocatalytic properties.

The exploration of new open-framework polyoxometalates is very significant in structural chemistry and materials science. Herein, three new organic hybrid three-dimensional vanadium borophosphates (HO)(Haeae){[Cd(HO)][HO⊃(VBPO)]}·15HO (1, aeae = 2-(2-aminoethylamino)ethanol) and (HO)(Haeae){[TM(HO)(Haeae)][HO⊃ (VBPO)]}·9HO [TM = Mn(2), Co(3)] were hydrothermally prepared and structurally characterized. The three vanadium borophosphates contain similar 12-member ring crown-shaped clusters [(VBPO)] based on the linkage of six [VO] dimers and six [BPO] units.

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.

Russian Doll-like 3d-4f Cluster Wheels with Slow Relaxation of Magnetization.

The solvothermal reactions of LnCl·6HO and MCl·6HO (M = Co, Ni) with 2,2'-diphenol (HL) and 5,7-dichloro-8-hydroxyquinoline (HL) gave three 3d-4f heterometallic wheel-like nano-clusters [LnM(L)(L)(-OH)(OCH)Cl(CHCN)]Cl·HO (Ln = Dy, M = Co, = 3 for ; Ln = Dy, M = Ni, = 0 for ; Ln = Tb, M = Ni, = 0 for ) with similar cluster structure. The innermost Ln(III) ion is encapsulated in a planar Ln ring which is further embedded in a chair-conformation M ring, constructing a Russian doll-like 3d-4f cluster wheel Ln(III)⸦Ln⸦M. and show obvious slow magnetic relaxation behavior with negligible opening of the magnetic hysteresis loop.

"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.

Electronic effects promoted the catalytic activities of binuclear Co(II) complexes for visible-light-driven CO reduction in a water-containing system.

Under the action of a catalyst, the photoinduced reduction of CO to chemicals and fuels is one of the greenest and environment-friendly approaches for decreasing atmospheric CO emissions. Since the environment was affected by the greenhouse effect, scientists have never stopped exploring efficient photoinduced CO reduction systems, particularly the highly desired non-noble metal complexes. Most of the currently reported complexes based on non-noble metals exhibit low catalytic activity, selectivity, and stability in aqueous systems under the irradiation of visible light.

Infrequent Cubane-Like Chromium Sulfide Cluster with σ-Donor Ligands with Efficient Electrocatalytic Property Toward Hydrogen Evolution Reaction.

The exploitation of efficient and economical electrocatalysts for hydrogen evolution reaction (HER) is of exceeding interest in renewable clean-energy technologies. Herein, the facile solvothermal reaction of S and chromic acetate in ethylenediamine (en) achieved a novel organic hybrid chromium sulfide [Cr(μ-S)(en)(SH)]·0.25HO (), which offers a new type of antiferromagnetic cubane-like chromium sulfide cluster with σ-donor en ligands.

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.

The strong and cytotoxicity of three new cobalt(II) complexes with 8-methoxyquinoline.

Three new cobalt(II) complexes, [Co(MQL)Cl] (CoCl), [Co(MQL)Br] (CoBr), and [Co(MQL)I] (CoI), bearing 8-methoxyquinoline (MQL) have been designed for the first time. MTT assays showed that CoCl, CoBr, and CoI exhibit much better antiproliferative activities than cisplatin toward cisplatin-resistant SK-OV-3/DDP and SK-OV-3 ovarian cancer cells, with IC values of as low as 0.32-5.

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.

Rare examples of hybrid chalcogenoarsenate(III) incorporating trivalent vanadium complexes.

A series of new hybrid vanadium chalcogenoarsenates(III) [V(en)AsS] (1, en = ethylenediamine), [V(dap)AsSe] (2, dap = 1,2-diaminopropane), [V(teta)AsQ] {Q = S (3) and Se (4), teta = triethylene-tetramine}, and [VIII2(en)(μ-O)][AsSe] (5) were solvothermally prepared and structurally characterized. The trigonal-pyramidal [AsQ] anions in 1-4 act as η-AsQ chelating ligands to the unsaturated trivalent vanadium complex cations [V(en/dap)]/[V(teta)], resulting in neutral molecules. 5 consists of a discrete saddle-like selenidoarsenate [AsSe] anion built up from corner-sharing [AsSe] trigonal pyramids and the dinuclear trivalent vanadium complex cation [VIII2(en)(μ-O)] constructed through two [V(en)] units bridged one μ-O group.

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.

Two Heterometallic Nanoclusters [DyNi] and [DyMnMn]: Structure, Assembly Mechanism, and Magnetic Properties.

A full understanding of the assembly mechanisms of coordination complexes is of great importance for a directional synthesis under control. We thus explored here the formation mechanisms of the two new heterometallic nanoclusters [DyNi(μ-OH)(L)(OAc)(HO)]·3.25EtOH·4CHCN () and [DyMnMnO(OH)(OAc)(L)(HL)(EtOH)]·2EtOH·2CHCN·2HO () with different cubane-based squarelike ring structures, which were obtained from the reactions of 4-bromo-2-[(2-hydroxypropylimino)methyl]phenol (HL) with Dy(NO)·6HO and the transition metal salt Ni(OAc)·4HO or Mn(OAc)·4HO.

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.