A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation.

Lanthanide-containing clusters are synthetically challenging and with significant chemical and materials applications. Herein, two isostructural heterometallic clusters of the formula (NO)@[LnNi(OH)(IDA)(CHCOO)(NO)(HO)]Cl⋅xHO⋅yCHOH (IDA=iminodiacetate; Ln=Gd 1, x=110, y=0; Ln=Eu 2, x=95, y=40) were obtained via co-hydrolysis of Ln (Gd or Eu) and Ni in the presence of iminodiacetate (IDA). Crystallographic studies show that each features a truncated tetrahedral core of LnNi within which a void of 1.

Unraveling the Intertwining Factors Underlying the Assembly of High-Nuclearity Heterometallic Clusters.

Two closely related yet distinctly different cationic clusters, [DyNi(HEIDA)(OH)(OAc)(HO)] (1) and [DyNi(HEIDA)(EIDA)(IDA)(OH)(OAc)(HO)] (2) (HEIDA=N-(2-hydroxyethyl)iminodiacetate), each featuring a multi-shell core of Platonic and Archimedean polyhedra, were obtained. Depending on the specific conditions used for the co-hydrolysis of Dy and Ni, the product can be crystallized out as one particular type of cluster or as a mixture of 1 and 2. How the reaction process was affected by the amount of hydrolysis-facilitating base and/or by the reaction temperature and duration was investigated.

A Cubic Tinkertoy-like Heterometallic Cluster with a Record Magnetocaloric Effect.

Clusters showing a giant magnetocaloric effect (MCE) are of interest as molecular coolants for magnetic refrigeration. Herein, we report two heterometallic clusters, denoted as and , just to highlight their inorganic core motifs, obtained by ligand-controlled co-hydrolysis of Ni and Ln (Ln = Gd, Sm) in the presence of -(2-hydroxyethyl)iminodiacetic acid (HHEIDA). Both clusters display fascinating cubic Tinkertoy-like structures, with the core motifs being built of multiple metallic shells of Platonic and Archimedean polyhedra.

Construction of a series of Ln-MOF luminescent sensors based on a functional "V" shaped ligand.

It is necessary to decrease the application cost of luminescent Ln-MOF sensors to develop multiple functionalities. The ingenious design of ligands and the rational doping of Ln ions are the main approaches to endowing Ln-MOFs with more functionalities. "V" shaped ligands can cause diamond pore channels commonly.

Anion-Guided Stepwise Assembly of High-Nuclearity Lanthanide Hydroxide Clusters.

The ability to construct complex molecular architectures with precise control is critical for realizing molecule-based materials and functions. Using the assembly of a 60-metal complex of Er with histidine as an example, we demonstrate the rational assembly of otherwise synthetically elusive polynuclear lanthanide hydroxide clusters directed by the combined set of I and CO as templates. We succeeded in the stepwise transformation starting from Er to Er by way of two key intermediates Er and Er .

Rare Silver-Histidine Cluster Complex and Its Single-Crystal-to-Single-Crystal Phase-Transition Behavior.

Silver complexes with proteinogenic amino acid ligands are of interest for biomedical and antimicrobial applications. In this work, we obtained {[Ag(l-his)](NO)·3HO}{[Ag(l-his)(HO)](NO)·3HO} () and {[Ag(d-his)](NO)·3HO}{[Ag(d-his)(HO)](NO)·3HO} (), which represent the first example of any Ag-exclusive complex featuring a cluster-type core motif and with only proteinogenic amino acid ligands. Upon immersion into acetonitrile, an interesting single-crystal-to-single-crystal transformation occurred to produce a new cluster complex of the formula [Ag(l-his)(NO)(HO)](NO) ().

Self-assembly of tetranuclear 3d-4f helicates as highly efficient catalysts for CO cycloaddition reactions under mild conditions.

A series of novel asymmetry 3d-4f helicates ZnLnL (HL = N-(2-((3,5-di-tert-butyl-2-hydroxybenzylidene)amino)ethyl)-2-hydroxybenzamide, Ln = Dy(1), Gd(2), Er(3)) were successfully constructed via selective incorporation of groups with different coordination capabilities. These helicates with the well-defined conformation demonstrate high catalytic efficiency in converting CO to cyclic carbonates under mild conditions. Particularly, ZnErL showed superior catalytic performance with high catalytic activity (TOF up to 38 000 h) and extraordinary selectivity (up to 99%) across the wide substrate scope.

Anion-induced 3d-4f luminescent coordination clusters: structural characteristics and chemical fixation of CO under mild conditions.

Two series of anion-induced 3d-4f luminescent clusters ZnII2LnIII2L4 (LnIII = Eu3+, Tb3+, Er3+, Yb3+, Nd3+) and ZnII4LnIII2L4 (LnIII = Tb3+, Nd3+) based on μ3-OH group were synthesized and characterized. The difference in anions not only leads to significant structural changes, but also changes the luminescent properties of the 3d-4f coordination clusters. These complexes show excellent catalytic performance for CO2 conversion to obtain cyclic carbonates with wide substrate scopes and high selectivity under mild conditions.

The Construction of Homochiral Lanthanide Quadruple-Stranded Helicates with Multiresponsive Sensing Properties toward Fluoride Anions.

A series of unique homochiral lanthanide tetranuclear quadruple-stranded helicates have been self-assembled controllably by using the intrinsic advantages of chiral bridging ligands, (S)-H L and (R)-H L, and lanthanide ions with high coordination numbers. The self-assembly process of these chiral helicates not only ensures the structural stability and quadruple-stranded feature of lanthanide cluster in the solid state and solution, but also achieves effective transfer and amplification of the chirality code from the ligand to a higher supramolecular level. Moreover, through using optical rotation, circular dichroism spectra analysis, and luminescence measurements, we demonstrate that these chiral lanthanide helicates could serve as sensitive and multi-responsive sensors to recognize and detect F anions based on the change of chiral signal and NIR luminescence simultaneously, which represents a meaningful exploration for developing functional lanthanide-based polynuclear clusters.

A "turn-on" lanthanide complex chemosensor for recognition of lead(ii) based on the formation of nanoparticles.

A functional amide-type pincer ligand was designed and synthesized, which could effectively capture Tb ions to form a phosphorescence complex-based chemosensor Tb-1. The chemosensor could further coordinate with Pb ions and display a turn-on phosphorescence response. This sensing process was analyzed in detail by steady-state luminescence spectroscopy, time-resolved luminescence spectroscopy, electron microscopy and dynamic light scattering, which suggest that the formation of Pb-induced hydroxide nanoclusters can adjust the optical signal of the external luminescence compound by embedment and fixation of Tb complexes.

A Multi-responsive Regenerable Europium-Organic Framework Luminescent Sensor for Fe , Cr Anions, and Picric Acid.

A novel luminescent microporous lanthanide metal-organic framework (Ln-MOF) based on a urea-containing ligand has been successfully assembled. Structural analysis revealed that the framework features two types of 1D channels, with urea N-H bonds projecting into the pores. Luminescence studies have revealed that the Ln-MOF exhibits high sensitivity, good selectivity, and a fast luminescence quenching response towards Fe , Cr anions, and picric acid.

K(+)-Induced in situ self-assembly of near-infrared luminescent membrane material armored with bigger Yb(III) complex crystallites.

A semi-rigid ligand could capture effectively Yb(3+) ions to form a stable Yb(3+) complex and provide a potential cavity to accommodate alkali metal ions. Only K(+) ions could induce the Yb(3+) complex to form a 1D coordination polymer and promote the in situ formation of an NIR membrane coated with bigger Yb(3+) complex crystallites under mild conditions.

Co@Co3O4 core-shell particle encapsulated N-doped mesoporous carbon cage hybrids as active and durable oxygen-evolving catalysts.

Cobalt-based nanomaterials are promising candidates as efficient, affordable, and sustainable alternative electrocatalysts for the oxygen evolution reaction (OER). However, the catalytic efficiency of traditional nanomaterials is still far below what is expected, because of their low stability in basic solutions and poor active site exposure yield. Here a unique hybrid nanomaterial comprising Co@Co3O4 core-shell nanoparticle (NP) encapsulated N-doped mesoporous carbon cages on reduced graphene oxide (denoted as Co@Co3O4@NMCC/rGO) is successfully synthesized via a carbonization and subsequent oxidation strategy of a graphene oxide (GO)-based metal-organic framework (MOF).

Turn-on phosphorescent chemodosimeter for Hg2+ based on a cyclometalated Ir(III) complex and its application in time-resolved luminescence assays and live cell imaging.

A novel "turn-on" phosphorescent chemodosimeter based on a cyclometalated Ir(III) complex has been designed and synthesized, which displays high selectivity and sensitivity toward Hg(2+) in aqueous media with a broad pH range of 4-10. Furthermore, by time-resolved photoluminescence techniques, some interferences from the short-lived background fluorescence can be eliminated effectively and the signal-to-noise ratio of the emission detection can be improved distinctly by using the chemodosimeter. Finally, the chemodosimeter can be used to monitor Hg(2+) effectively in living cells by confocal luminescence imaging.