Au/Ag@polyoxometalate core-shell structures: from nanoparticles to atomically precise nanoclusters.

This review summarizes the progress in the research on polyoxometalate (POM)-decorated gold (Au) and silver (Ag) core-shell structures (Au/Ag@POMs), emphasizing their substantial application potential in catalysis, medicine, and biology. It outlines the central strategies for fabricating Au/Ag@POMs with diverse morphologies and dimensions, leveraging POMs as protective ligands and reducing agents as well as for ligand exchange. Of particular note is the focus on the analysis of the nanoparticle size, shape, and intricate architecture of POM shells using cryo-electron microscopy techniques.

Enantioselective Synthesis of Homochiral Hierarchical NdFe-Oxo Cluster from Racemic NdFe-Oxo Cluster.

Enantioselective synthesis of homochiral rare earth clusters is still a great challenge. In this work, we developed an efficient "cluster to cluster" approach, that is, a pair of enantiomerical /-{NdFe}-oxo clusters were successfully obtained from the presynthesized racemic {NdFe}-oxo cluster. /-hydrobenzoin ligands trigger the transformation of the pristine clusters by an SN-like mechanism.

Selective Passivation of Surface toward Bright Yellow Defective Emission of CdS Quantum Dots.

CdE (E = S, Se) quantum dots (QDs) with a broad and large Stokes shift PL emission have emerged as potential materials for white-light LEDs. However, this surface-related emission of nanocrystals is currently limited by low quantum efficiency. Herein, a convenient noninjected one-pot method at a relatively low temperature to prepare CdS QDs was readily achieved.

Doping transition metals to modulate the chirality and photocatalytic activity of rare earth clusters.

In this paper, we report the successful assembly of achiral {LnM} ([LnM(μ-OH)(acac)(CHO)(CHOH)], Ln = La, M = Mn, Co, Fe) and chiral {NdFe} ([NdFe(μ-O)(μ-OH)(acac)(NO)(CHOH)(HO)]) rare earth clusters using achiral rigid ligands and a transition metal doping strategy. {LnM} can be viewed as the fusion of two {LnM} tetrahedrons by sharing vertices. {NdFe} results from the fusion of four {LnM} tetrahedrons by vertice and edge sharing.

A chloride-doped silver-sulfide cluster [AgSCl(CCBu)]: hierarchical assembly, enhanced luminescence and cytotoxicity to cancer cells.

The formation of high-nuclear silver(I) clusters remains elusive and their potential applications are still underdeveloped. Herein, we report an unprecedented gigantic Ag ([AgSCl(CCBu)](SbF)) cluster co-templated by Cl and S, which was well-defined by single-crystal X-ray diffraction and high-resolution mass spectrometry. The cluster exhibits a hierarchical structure consisting of fused AgX kernel, AgX shell and "cluster of clusters assembling" of four pentagonal concave polyhedral {AgX} units.

Unusual structural transformation and luminescence response of magic-size silver(I) chalcogenide clusters ligand-exchange.

Structural transformations of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure-property correlation. Here, we present an alkynyl ligand-exchange induced growth of atomically precise silver(I) clusters, which are particularly of interest because of their luminescence response at room temperature. SCXRD and UV-vis map out the growth steps of the cluster from [AgS(CCBu)] featuring a pseudo- concave AgS to [AgS(CCPhBr)] with a pseudo- core-shell AgS@Ag@Ag, which is driven by a thermodynamic route under the disruption of ligands.

Solvent-driven crystal-crystal transformation and morphology change in a 2D layered inorganic POM-based framework.

In this paper, a pure 2D inorganic POM-based framework underwent a single crystal to single crystal conversion when soaked in organic solvents that are miscible with water, forming a more densely packed identical framework accompanying the formation of nanowires. The change in morphology is closely related to the surface tension of water, and the lower surface tension achieved by dehydration promotes the formation of nanowires, which is revealed by SXRD, PXRD, SEM, TGA and electrochemical impedance spectroscopy (EIS).

Cluster From Cluster: A Quantitative Approach to Magic Gold Nanoclusters [Au (SR) ].

High-yield and large-scale synthesis are highly demanded for the studies of gold nanoclusters. We developed a "cluster from cluster" approach to assemble gold nanoclusters with preformed atomically precise Au precursors. This facile approach has proved to be very effective in the synthesis of the well-known magic cluster [Au (SR) ] , which could prepare the target cluster in high yield (overall yield up to ≈100 %) at large scale (gram-scale based on gold).

A nonconventional host-guest cubic assembly based on γ-cyclodextrin and a Keggin-type polyoxometalate.

Supramolecular self-assembly allows components to organize themselves into regular patterns by using non-covalent interactions to find the lowest-energy configuration. However, self-assembling organic and inorganic building blocks together into an ordered framework remains a challenge due to the difficulties in rationally interfacing two dissimilar materials. Herein, we report on the host-guest ensemble of polyoxometalates (POMs) using cyclodextrins (CDs) as the trapping agent to form POM@γ-CD entities.

Assembly of silver alkynyl compounds with various nuclearities.

A convenient method for the synthesis of silver alkynyl compounds containing different nuclearities has been developed. The reaction of AgC[triple bond, length as m-dash]CBu(t) and AgX (X = CF3CO2(-), C2F5CO2(-)) in the presence of auxiliary ligands L (L = bipyridine, bipy; 1,10-phenanthroline, phen; 2-(diphenylphosphino)pyridine, dppy) under different conditions afforded a family of new silver alkynyl compounds, namely, [Ag3(bipy)(C[triple bond, length as m-dash]CBu(t))(CF3CO2)2]n (), [Ag4(bipy)2(C[triple bond, length as m-dash]CBu(t))(CF3CO2)3]n (), [Ag6(phen)3(C[triple bond, length as m-dash]CBu(t))2(C2F5CO2)4(MeOH)(EtOH)] (), [Ag8L4(C[triple bond, length as m-dash]CBu(t))2(C2F5CO2)6] (L = bipy, ; L = phen, ), [Ag10(dppy)2(C[triple bond, length as m-dash]CBu(t))6X4] (X = CF3CO2(-), ; X = C2F5CO2(-), ), [Ag12(bipy)2(C[triple bond, length as m-dash]CBu(t))8(C2F5CO2)4] () and [Ag12(phen)4(C[triple bond, length as m-dash]CBu(t))6(CF3CO2)6]·2EtOH (). Single-crystal X-ray analysis revealed that compounds and display infinite-chain structures, while the other seven compounds are discrete molecules containing silver nuclearities varying from 6 to 12.

Cluster linker approach: preparation of a luminescent porous framework with NbO topology by linking silver ions with gold(I) clusters.

A cluster-based luminescent porous metal-organic framework has been constructed through a "cluster linker" approach. The luminescent gold(I) cluster, prefunctionalized with pyrazinyl groups, was used as a cluster linker, similar to an organic linker, to connect silver ions in order to form a 3D framework. 1D channels with 1.

[Ag(70)(PW(9)O(34))(2)((t)BuC[triple bond, length as m-dash]C)(44)(H(2)O)(2)](8+): ionothermal synthesis of a silver cluster encapsulating lacunary polyoxometalate ions.

A silver alkynyl cluster containing a Ag70 shell and two lacunary [PW9O34](9-) templating ions was synthesized by an ionothermal approach. Fast core-shell electronic communication between silver(i) centers and polyoxometalates was verified via cyclic voltammetry studies in [BMIm]BF4.

Poly[[bis-(2,2-bipyridine)-bis-[μ(6)-5-(carboxyl-atometh-oxy)benzene-1,3-dicarboxyl-ato]trimanganese(II)] monohydrate].

The title compound, {[Mn(3)(C(10)H(5)O(7))(2)(C(10)H(8)N(2))(2)]·H(2)O}(n), was synthesized under hydro-thermal conditions. Six carboxyl-ate groups of six 5-(carboxyl-atometh-oxy)benzene-1,3-dicarboxyl-ate anions (OABDC(3-)) join three Mn(II) ions into a trinuclear centrosymmetric [Mn(3)(μ(2)-COO)(6)] unit with one Mn site situated on a centre of inversion. The latter Mn(II) ion exhibits a distorted MnO(6) coordination, whereas the other Mn(II) ion has a trigonal-bipyramidal MnN(2)O(3) coordination environment resulting from three carboxylate O atoms and the two N atoms of the bipyridine ligand.