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Formation of Complex Ions03:45

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Crystal Field Theory
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Deciphering icosahedra structural evolution with atomically precise silver nanoclusters.

Feng Hu1, Gaoyuan Yang2, Lu-Ming Zheng1

  • 1Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education), Tsinghua University, Beijing, P. R. China.

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Summary

Researchers synthesized giant silver nanoclusters (Ag213 and Ag429) using ligand engineering. These precisely structured clusters reveal layer-by-layer growth pathways for multiply-twinned icosahedral nanoparticles.

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Inorganic Chemistry

Background:

  • Determining nanoparticle (NP) atomic structure is key to understanding their evolution and properties.
  • Controlling the growth of multiply-twinned metal NPs is challenging due to competing pathways.

Purpose of the Study:

  • To report the synthesis of two giant silver icosahedral nanoclusters.
  • To elucidate the structural evolution and properties of these novel nanoclusters.

Main Methods:

  • Ligand engineering and kinetic control for nanocluster synthesis.
  • Single-crystal X-ray diffraction for atomic structure determination.
  • Spectroscopic and dynamic measurements to confirm metallic nature.

Main Results:

  • Synthesis of two giant silver nanoclusters: [Ag213(C≡CR1)96]5- (Ag213) and [Ag429Cl24(C≡CR2)150]5- (Ag429).
  • Atomic structures reveal multilayered icosahedral cores: Ag141|(Ag13@Ag42@Ag86) for Ag213 and Ag297 (Ag13@Ag42@Ag92@Ag150) for Ag429.
  • Ag429, with 260 valence electrons, is the largest reported Ag0-containing nanocluster; both exhibit metallic properties.

Conclusions:

  • The atomically precise structures provide insights into the layer-by-layer evolution from nuclei to seeds of silver icosahedra.
  • Demonstrates successful control over the growth of complex multiply-twinned silver nanoclusters.