Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18](-) cluster (SR: thiolate) using a pure [Ag25(SR)18](-) cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag(25-x)Au(x)(SR)18](-), x=1-8. Mass spectrometry and crystallography of [Ag24Au(SR)18](-) reveal the presence of the Au heteroatom at the Ag25 center, forming Ag24Au. The successful exchange of the central Ag of Ag25 with Au causes perturbations in the Ag25 crystal structure, which are reflected in the absorption, luminescence, and ambient stability of the particle. These properties are compared with those of Ag25 and Ag24Pd clusters with same ligand and structural framework, providing new insights into the modulation of cluster properties with dopants at the single-atom level.
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http://dx.doi.org/10.1002/anie.201509381 | DOI Listing |
Acc Chem Res
August 2024
Department of Materials Science and Engineering, University of California, Irvine, California 92697, United States.
ConspectusDNA-stabilized silver nanoclusters (Ag-DNAs) are sequence-encoded fluorophores. Like other noble metal nanoclusters, the optical properties of Ag-DNAs are dictated by their atomically precise sizes and shapes. What makes Ag-DNAs unique is that nanocluster size and shape are controlled by nucleobase sequence of the templating DNA oligomer.
View Article and Find Full Text PDFJ Am Chem Soc
February 2024
Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Atom-precise metal nanoclusters (NCs) with large bulk (nuclearity >60) are important species for insight into the embryonic phase of metal nanoparticles and their top-down etching synthesis. Herein, we report a metastable rod-shaped 70-nuclei copper-hydride NC, [Cl@CuH(PhC≡C)(CFCOO)] (), with Cl as the template, in which the Cl@Cu kernel adopts a distinctive metal packing mode along the bipolar direction, and the protective ligand shell exhibits corresponding site differentiation. In terms of metal nuclearity, is the largest alkynyl-stabilized Cu-hydride cluster to date.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2024
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan, 250100, P. R. China.
Polyoxometalates (POMs) represent crucial intermediates in the formation of insoluble metal oxides from soluble metal ions, however, the rapid hydrolysis-condensation kinetics of Mo or W makes the direct characterization of coexisted molecular species in a given medium extremely difficult. Silver nanoclusters have shown versatile capacity to encapsulate diverse POMs, which provides an alternative scene to appreciate landscape of POMs in atomic precision. Here, we report a thiacalix[4]arene protected silver nanocluster (Ag72b) that simultaneously encapsulates three kinds of molybdates (MoO , Mo O and Mo O ) in situ transformed from classic Lindqvist Mo O , providing more deep understanding on the structural diversity and condensation growth route of POMs in solution.
View Article and Find Full Text PDFTo acquire the atomic design of new functional Ag(i) nanoclusters (NCs), a new synthetic approach of site-specific alloying has been unveiled, by which the neutral CO templated Ag core is confined through Cu containing two peripheral motif units. The impact of surface charge, size and shape of the template on the self-assembly of Ag(i) has been precisely controlled here for the first time and as a result, a similar pentagonal gyrobicupola-like Ag core is formed while varying the templates (S, CO and CO). However, the surface charge generated on the Ag(i) core due to the presence of a neutral template opens up the possibility of this novel alloying process.
View Article and Find Full Text PDFAnal Chem
March 2022
Department of Chemistry and Biology, Faculty of Environment and Life Science, Beijing University of Technology, Beijing 100124, China.
Differential expression of RNA splice variants among individual cells accounts for cell heterogeneity of gene expression, which plays a key role in the regulation of the immune system. However, currently available techniques face difficulties in achieving single-cell analysis of RNA splice variants with high base resolution, high spatial resolution and accurate quantification. Herein, we constructed DNA-templated dual-functional nanocluster probes to achieve in situ imaging and accurate quantification of RNA splice variants at the single-cell level.
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