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An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
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An allyl group is a three-carbon conjugated system where the sp³-hybridized allylic carbon is bonded to a CH=CH2 group via a single bond. Allyl anions can be obtained by treating propene with a strong base that can deprotonate methyl groups. Allyl cations are formed as intermediates during substitution reactions involving allylic halides. In both cases, the hybridization of the allylic carbon changes from sp3 to sp2, giving rise to a carbon chain with three sp2-hybridized carbons, each with...
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The fragmentation of alkynes preferentially occurs at the carbon–carbon bond between the α and β carbon of the alkyne bond to generate a 3-propynyl cation (or propargyl cation). In terminal alkynes, there is the only type of fragmentation that yields the 3-propynyl cation. The unsubstituted 3-propynyl cation exhibits a peak at a mass-to-charge ratio of 39. In internal alkynes, the 3-propynyl cation is substituted. For example, 2-pentyne fragments into methyl-substituted 3-propynyl cation,...
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An Atomically Precise Alkynyl-Protected PtAg42 Superatom Nanocluster and Its Structural Implications.

Hui Shen1, Tsutomu Mizuta1

  • 1Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-hiroshima, 739-8526, Japan.

Chemistry, an Asian Journal
|October 4, 2017
PubMed
Summary

Researchers synthesized and characterized a novel platinum-doped silver superatom nanocluster. This study reveals a unique Russian doll structure, a missing silver shell, and unprecedented protective roles for alkynyl and hexafluoridophosphate anions.

Keywords:
alkynesdopingicosidodecahedronssilver nanoclusterssuperatoms

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Area of Science:

  • * Inorganic Chemistry
  • * Materials Science
  • * Nanotechnology

Background:

  • * Superatom nanoclusters (SNCs) exhibit unique properties due to their electronic shell structure.
  • * The synthesis and structural elucidation of complex, multi-metal SNCs remain a significant challenge.
  • * Understanding the protective ligands and their interaction with the cluster core is crucial for stability and functionality.

Purpose of the Study:

  • * To synthesize and determine the crystal structure of a novel Pt-doped Ag superatom nanocluster.
  • * To investigate the structural arrangement of the metallic core and the surface ligands.
  • * To explore the unprecedented protective role of SbF6- anions in SNCs.

Main Methods:

  • * Single-crystal X-ray diffraction for precise structure determination.
  • * Synthesis of the alkynyl-protected Pt-doped Ag superatom nanocluster.
  • * Spectroscopic and analytical techniques for characterization.

Main Results:

  • * Successful synthesis and structure determination of [PtAg42(C≡CC6H4CH3)28](SbF6)6 (1).
  • * Discovery of a concentric three-shell Pt@Ag12@Ag30 core, including a previously missing icosidodecahedral Ag30 shell and a novel M43 unit.
  • * Identification of co-protection by alkynyl ligands and SbF6- anions, with SbF6- exhibiting an unprecedented protective role.
  • * Observation of unique alkynyl ligand connectivity through pentagonal faces to both inner and outer silver shells.

Conclusions:

  • * The crystal structure determination of nanocluster 1 reveals the missing Ag30 shell and a novel M43 structural unit.
  • * SbF6- anions play an unprecedented protective role in stabilizing the nanocluster.
  • * The study demonstrates unique ligand penetrability through pentagonal faces, offering new insights into SNC design and stabilization.