Bottom-up construction of chiral metal-peptide assemblies from metal cluster motifs.

The exploration of artificial metal-peptide assemblies (MPAs) is one of the most exciting fields because of their great potential for simulating the dynamics and functionality of natural proteins. However, unfavorable enthalpy changes make forming discrete complexes with large and adaptable cavities from flexible peptide ligands challenging. Here, we present a strategy integrating metal-cluster building blocks and peptides to create chiral metal-peptide assemblies and get a family of enantiopure [R-/S-NiL] (n = 2, 3, 6) MPAs, including the R-/S-NiL capsule, the S-NiL trigonal prism, and the R-/S-NiL octahedron cage.

Ln/Cu Bimetallic Nanoclusters with Enhanced NIR-II Luminescence.

Coinage-metal clusters with excellent luminescence properties have attracted considerable interest due to their intriguing structures and potential applications. However, achieving strong near-infrared (NIR) luminescence in these clusters is highly challenging. Here, we have successfully synthesized the first Ln/Cu bimetallic clusters, formulated as [LnCuOCl(2-MeO-PhC≡C)] (ClO) (Ln = Yb for , Er for , and Gd for ).

Strong NIR-II Magneto-Optical Activity of a Chiral SmCu Cage.

The magneto-optical response of chiral materials holds significant potential for applications in physics, chemistry, and biology. However, exploration of the near-infrared (NIR) magneto-optical response remains limited. Herein, we report the synthesis and strong NIR-II magneto-optical activity of three pairs of chiral 34 clusters of (Ln = Sm, Gd, and Dy).

High-Nuclearity LnAl Clusters: Neonates of Open Hollow Dodecahedral Cage Families.

Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, [LnAl(μ-OH)(μ-OH)(OAc)(HO)](ClO)·(MeCN)·(HO), (Ln = Dy and = 27, = 300 for ; Ln = Y and = 28, = 420 for ). Remarkably, the 350 metal atoms in and display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron.

An Unusual Crystalline Porous Framework Constructed from Multitypes of Cages with Proton Conduction Property and Heterogeneous Catalytic Activity for Pyrazole Synthesis.

An unusual crystalline porous framework constructed from four types of cages, including all-inorganic Keggin-type polyoxometalate (POM) cages [HWO], organic hexamethylenetetramine (Hmt) cages, nanosized silver-Hmt coordination cages, and giant POM-silver-Hmt cages, was hydrothermally synthesized and structurally characterized. The framework features a highly symmetrical structure with one-dimensional nanoscale channels and holds good thermal/solvent stability, which endow it with proton conduction properties and heterogeneous catalytic activity for pyrazole. This paper not only contributes to broadening the structural diversity of cage-based crystalline porous framework materials but also sheds new light on the design of new functional framework materials.

An organophosphate 3d-4f heterometallic polyoxoniobate nanowire.

Four different structural compositions of organophosphate, 3d transition metal, 4f lanthanide and polyoxoniobate (PONb) are unified in a system for the first time to form a new type of organophosphate 3d-4f heterometallic inorganic-organic hybrid PONb nanowire. Interesting magnetic anisotropy and slow magnetic relaxation are found in the PONb nanowire.

Enhancement of Magneto-Chiral Dichroism Intensity by Chemical Design: The Key Role of Magnetic-Dipole Allowed Transitions.

Here we report on the strong magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption up to 5.0 T on {ErNi} metal clusters obtained by reaction of enantiopure chiral ligands and Ni and Er precursors. Single-crystal diffraction analysis reveals that these compounds are 34 heterometallic clusters, showing helical chirality.

Magneto-optical Properties of Chiral CoLn and CoLn (Ln = Dy and Er) Clusters.

A series of chiral heterometallic Ln-Co clusters, denoted as and (Ln = Dy and Er), were synthesized by reacting the chiral chelating ligand (/)-2-(1-hydroxyethyl)pyridine (Hmpm), CoAc·4HO, and Ln(NO)·6HO. and exhibit perfect mirror images in circular dichroism within the 320-700 nm range. Notably, the and clusters display pronounced magnetic circular dichroism (MCD) responses of the hypersensitive f-f transitions I-G at 375 nm and I-H at 520 nm of Er ions.

Tuning Electrocatalytic Water Oxidation Activity: Insights from the Active-Site Distance in LnCu Clusters.

Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu, abbreviated as LnCu-AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu-IM (Ln = La and Nd; IM = Imidazole), and LnCu-IDA (Ln = Nd; HIDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu ions around one Ln ion in LnCu, with variations in Cu···Cu distances attributed to different ligands.

Soluble GdCu clusters: effective molecular electrocatalysts for water oxidation.

The water oxidation half reaction in water splitting for hydrogen production is extremely rate-limiting. This study reports the synthesis of two heterometallic clusters (GdCu-IM and GdCu-AC) for application as efficient water oxidation catalysts. Interestingly, the maximum turnover frequency of GdCu-IM in an NaAc solution of a weak acid (pH 6) was 319 s.

Exploration and Insights on Topology Adjustment of Giant Heterometallic Cages Featuring Inorganic Skeletons Assisted by Machine Learning.

Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, the sensitive coordination bonds and vast synthetic space have limited their systematic exploration. Herein, two giant cage-like clusters featuring the organic ligand-directed inorganic skeletons of Ni[LaNi(IDA)(OH)(CO)(HO)]·(NO)·(HO) (, 5 × 5 × 3 - CO) and [LaNi(IDA)(OH)(CO)(NO)(HO)]·(NO)·(HO) (, 5 × 5 × 5 - CO) were discovered by a high-throughput synthetic search.

Uranyl Polyoxotungstate Cluster for Visible-Light-Driven Heterogeneous C-H Selective Fluorination.

The selective fluorination of C-H bonds at room temperature using heterogeneous visible-light catalysts is both interesting and challenging. Herein, we present the heterogeneous sandwich-type structure uranyl-polyoxotungstate cluster Na{Na@[(SbWO)(UO)(POOH)]}·46HO (denoted as ) to regulate the selective fluorination of the C-H bond under visible light and room temperature. This is the first report in which uranyl participates in the fluorination reaction in the form of an insoluble substance.

From Helices to Crystals: Multiscale Representation of Chirality in Double-Helix Structures.

Single crystals with chiral shapes aroused the interest of chemists due to their fascinating polarization rotation properties. Although the formation of large-scale spiral structures is considered to be a potential factor in chiral crystals, the precise mechanism behind their formation remains elusive. Herein, we present a rare phenomenon involving the multitransfer and expression of chirality at micro-, meso-, and macroscopic levels, starting from chiral carbon atoms and extending to the double-helical secondary structure, ultimately resulting in the chiral geometry of crystals.

Conductive Lanthanide Metal-Organic Frameworks with Exceptionally High Stability.

Electrically conductive metal-organic frameworks (MOFs) have been extensively studied for their potential uses in energy-related technologies and sensors. However, achieving that goal requires MOFs to be highly stable and maintain their conductivity under practical operating conditions with varying solution environments and temperatures. Herein, we have designed and synthesized a new series of {[Ln(μ-O)(μ-OH)(INA)(GA)](CFSO)(HO)} (denoted as , Ln = Gd, Tm, and Lu, INA = isonicotinic acid, GA = glycolic acid) single crystals, where electrons are found to transport along the π-π stacked aromatic carbon rings in the crystals.

Exploring Diversity through Dimerization in Natural Products by a Rational Tandem Mass-Based Molecular Network Strategy.

The step- and atom-efficient dimerization strategy is frequently used in nature to build structural complexity and diversity. We propose the rationale and structural features of the versatile monomers that are responsible for "diversity through dimerization". Using 5-FAM-maleimide combined with a UHPLC-MS/MS-FBMN workflow, we successfully identified a diverse set of dimeric natural products from fungus F01315, in which all four complex 4'5-ring scaffolds are derived from one monomeric epoxyquinol and endowed with functional diversity.

Dual-Responsive Triple-Synergistic Fe-MOF for Tumor Theranostics.

The intelligent responsive drug delivery system has great application potential in cancer precision therapy. Although many antitumor methods have been developed based on drug delivery systems, most of them yet suffer from poor antitumor efficiency. In this project, a near-infrared and pH dual-response multimodal collaborative platform for diagnosis and treatment (PCN-DOX@PDA) was constructed.

Circularly polarized luminescence and performance modulation of chiral europium-titanium (EuTi)-oxo clusters.

The designed synthesis of chiral luminescent molecules with excellent circularly polarized luminescence (CPL) performance and high quantum yield (QY) levels has attracted great interest but remains very challenging. Herein, we report three pairs of chiral europium-titanium-oxo clusters featuring both modest CPL characteristics and high QY levels (up to 79%), which can be regulated by switching between different ligand substituents.

Interplay between anisotropy and magnetic exchange to modulate the magnetic relaxation behaviours of phenoxo bridged Dy dimers with axial β-diketonate co-ligands.

A series of Schiff base LH (()-2-((pyridin-2-ylmethylene)amino)phenol) supported phenoxo bridged symmetric [Dy(L)(hfac)] (1), [Dy(L)(tfac)] (2) and asymmetric [Dy(L)(thd)(NO)]·1.5HO (3) binuclear complexes were isolated using differently substituted β-diketonate co-ligands (Hhfac = hexafluoroacetylacetonate, Htfac = trifluoroacetylacetonate, and Hthd = 2,2,6,6-tetramethyl-3,5-heptanedione). In all the three complexes 1-3, the two LH ligands provide phenoxo bridging and N-donor atoms.

From a Metal-Organic Square to a Robust and Regenerable Supramolecular Self-assembly for Methane Purification.

Porous supramolecular assemblies constructed by noncovalent interactions are promising for adsorptive purification of methane because of their easy regeneration. However, the poor stability arising from the weak noncovalent interactions has obstructed their practical applications. Here, we report a robust and easily regenerated polyhedron-based cationic framework assembled from a metal-organic square.

Photoluminescence of Lanthanide-Titanium-Oxo Clusters and Based on a β-Diketone Ligand.

A series of acetylacetone-protected lanthanide-titanium-oxo clusters (LTOCs), formulated as [LaTi(μ-OH)(acac)(CHO)(CHOH)] (; Hacac = acetylacetone) and [LnTi(μ-O)(μ-OH)(acac)(CHO)(CHOH)] [Ln = Eu () and Tb ()], were synthesized through the reactions of LnCl·6HO (Ln = La, Eu, and Tb), Hacac, Ti(OPr), and triethylamine in methanol. Crystal structural analysis shows that exhibits an hourglass-like structure consisting of two LaTi cubane subunits by sharing one Ti ion, while can be viewed as a combination of four EuTi cubane subunits by sharing three corners and one side. The photoluminescence (PL) measurements show that exhibits excellent PL properties with a high quantum yield (QY) of 34.

Functionalization of Keggin Fe-Oxo Clusters.

Two Keggin Fe-oxo clusters, [PrFe(NO)(L-van)(D-van)(TEOA)(μ-OH)(μ-OH)(μ-O)(HO)]·(ClO)·(NO)·10HO () and [DyFe(NO)(L-van)(D-van)(TEOA)(μ-OH)(μ-OH)(μ-O)(HO)]·(ClO)·(NO)·15HO (), where L-van = l-valine, D-van = d-valine, and TEOA = triethanolamine, were prepared by using Ln as a stabilizer. Cluster crystallizes in a chiral space group of 2, while cluster crystallizes in a centrosymmetric space group of . Dynamic magnetic measurements of under a zero direct-current field reveal that exhibits single-molecule-magnet characteristics with an energy barrier of 18.

Magnetic 3d-4f Chiral Clusters Showing Multimetal Site Magneto-Chiral Dichroism.

Here, we report the molecular self-assembly of hydroxido-bridged {LnNi} ((Ln = Dy, Y) metal clusters by the reaction of enantiopure chiral ligands, namely, (/)-(2-hydroxy-3-methoxybenzyl)-serine), with Ni and Ln precursors. Single-crystal diffraction analysis reveals that these compounds are isostructural sandwich-like 3d-4f heterometallic clusters showing helical chirality. Direct current magnetic measurements on {DyNi} indicates ferromagnetic coupling between Dy and Ni centers, whereas those on {YNi} denote that the Ni centers are antiferromagnetically coupled and/or magnetically anisotropic.

Association between miRNA-499 gene polymorphism and autoimmune diseases: A meta-analysis.

Introduction: The association between miRNA-499 rs3746444 and a variety of autoimmune diseases has been reported. However, these results were contradictory and just focused on one or two autoimmune diseases. The present study aims to examine the possible association between rs3746444 polymorphism and the risk of autoimmune diseases.

Counterintuitive Lanthanide Hydrolysis-Induced Assembly Mechanism.

The understanding of the hydrolysis mechanism of lanthanide ions is limited by their elusive coordination configuration and undeveloped technology. A potential solution by high-resolution mass spectroscopy studies is hindered by the lack of a stable model under electrospray ionization (ESI) conditions and the complexity of the spectra. Herein, it is demonstrated that diketonate ligands can efficiently stabilize the hydrolyzed intermediate cluster of Ln under ESI conditions, and an effective mass difference fingerprint of isomorphism (MDFI) method is proposed, which can allow the determination of the nuclearity-number of the species without depth resolution.