Designing pillar-layered metal-organic frameworks with photo-induced electron transfer interactions between ligands for enhanced photodynamic sterilization and photocatalytic degradation of dyes and antibiotics.

Pollution caused by antibiotics, bacteria, and organic dyes presents global public health challenges, posing serious risks to human health. Consequently, new, efficient, fast, and simple photocatalytic systems are urgently required. To this end, 2,7-di(pyridin-4-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NDI)-an electron acceptor-is introduced as a connecting column into a porphyrin-based metal-organic layer (2DTcpp) with excellent photocatalytic activity; this modification yields a three-dimensional pillar-layered metal-organic framework (MOF, 3DNDITcpp) with superior photocatalytic reactive oxygen species (ROS) generation capability.

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.

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.

"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.

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.

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.

Ubiquitin-specific protease 3 attenuates interleukin-1β-mediated chondrocyte senescence by deacetylating forkhead box O-3 via sirtuin-3.

Osteoarthritis (OA) affects approximately 12% of the aging Western population. The sirtuin/forkhead box O (SIRT/FOXO) signaling pathway plays essential roles in various biological processes. Despite it has been demonstrated that ubiquitin-specific protease 3 (USP3) inhibits chondrocyte apoptosis induced by interleukin (IL)-1β, the role of USP3/SIRT3/FOXO3 in the senescence of chondrocytes in OA is unclear.

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.

Lanthanide nitrato complexes bridged by the bis-tridentate ligand 2,3,5,6-tetra(2-pyridyl)pyrazine: Syntheses, crystal structures, Hirshfeld surface analyses, luminescence properties, DFT calculations, and magnetic behavior.

Six dinuclear lanthanide(III) nitrato complexes [Ln(NO)(HO)](-tppz) (where tppz = 2,3,5,6-tetra(2-pyridyl) pyrazine and Ln(III) = Nd (), Sm (), Eu (), Gd (), Tb (), and Dy ()) with bis-tridentate N-heterocyclic 2,3,5,6-tetra(2-pyridyl)pyrazine as bridging ligand have been solvothermally synthesized and characterized via elemental analysis, infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. The 3-D Hirshfeld surface and 2-D fingerprint plots show that the main interactions in - are the O⋯H/H⋯O intermolecular interactions with relative contributions of about 62%. Although the poor lanthanide(III)-centered luminescence properties clearly point to the efficiency of nonradiative quenching processes (presence of water molecules in the coordination sphere of the lanthanide(III) ions), the ligand tppz is better suited to sensitize the lanthanide(III)'s emissions of Eu and Nd than Sm, Tb, and Dy.

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.

A green separation process of Ag a Ti(embonate) cage.

From an environmental perspective, silver recovery through a green process is imperative. In this work, a green supramolecular separation process of Ag has been developed by using a highly charged anionic Ti4L6 (L = embonate) cage as the extractant. Such a Ti4L6 cage has unique selectivity toward [Ag(NH3)2]+ ions, because only linear [Ag(NH3)2]+ ions can be trapped into the windows of the Ti4L6 cage, which is demonstrated by single-crystal X-ray diffraction analysis.

Rationally Designing Metal-Organic Frameworks Based on [Ln] Magnetic Building Blocks Utilizing 2-Hydroxyisophthalate and Fine-Tuning the Magnetic Properties of Dy Analogues by Terminal Coordinated Solvents.

By utilizing the 2-hydroxyisophthalic acid (HipO) ligand, 2D metal-organic frameworks (MOFs) featuring rare O-bridged [Ln]-magnetic building blocks (MBBs), [Ln(ipO)(DMF)(HO)] [Ln = Gd (), Dy (); DMF = ,-dimethylformamide], were rationally designed and synthesized. When the reaction solvents that behave as terminal ligands were changed, the coordination geometries of Ln ions and the arrangement fashion of [Ln]-MBBs for these MOFs were modified accordingly. Another type of 2D MOF of [Ln(ipO)(HO)]·2HO [Ln = Gd (), Dy ()] was thus obtained.

Dy single-molecule magnets from ligands incorporating both amine and acylhydrazine Schiff base groups: the centrosymmetric {Dy} displaying dual magnetic relaxation behaviors.

The novel multidentate chelating ligands N'-(2-pyridylmethylidene)-2-(2-pyridylmethylideneamino)benzohydrazide (Hpphz) and N'-(2-salicylmethylidene)-2-(2-salicylmethylideneamino)benzohydrazide (Hsshz), which incorporate both amine and acylhydrazine Schiff base groups, were synthesized and investigated in Dy coordination chemistry. The reactions of Hpphz and Dy(OAc)·4HO have yielded two {Dy} featuring double OAc bridges: [Dy(Haphz)(OAc)(ROH)] [R = Me (1) and Et (2)], where the Hpphz ligands were in situ hydrolyzed into 2-amino-(2-pyridylmethylideneamino)benzohydrazide ions (Haphz). Besides, the reaction between Hsshz and Dy(NO)·6HO afforded a [Dy(sshz)(μ-OH)(μ-O)(MeOH)]·17.

Self-Assembly of a Ti(embonate) Cage toward Silver.

Herein we report a variety of supramolecular architectures that are self-assembled by the highly charged anionic TiL (L = embonate) cages and noble-metal Ag ions in the presence of the different ligands, including six TiL-Ag(PPh) cages in whose structures the TiL cage catches various in situ formed [Ag(PPh)] moieties by a coordination bond and one cocrystal superstructure of a TiL cage with an in situ generated [Ag(PhP(CH)PPh)] cage via supramolecular interactions. In addition, the third-order nonlinear-optical properties of these compounds are investigated in detail.