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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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Silsesquioxane-Protected Silver Superatom.

Chengkai Zhang1, Fahri Alkan2, Wei-Dan Si1

  • 1School of Chemistry and Chemical Engineering, Key Lab of Colloid and Interface Chemistry, Ministry of Education, Shandong University, 250100 Ji'nan, People's Republic of China.

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|April 24, 2026
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Summary
This summary is machine-generated.

Researchers developed the first silsesquioxane-protected superatomic silver nanocluster (Ag40) using an adaptive synthesis. This breakthrough overcomes limitations in silver coordination chemistry and enables new silica-supported superatom synthesis.

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Inorganic Chemistry

Background:

  • Silsesquioxanes are versatile organic-inorganic hybrids used in metal complexes.
  • Their application in silver nanoclusters remained unexplored, posing challenges due to hard and soft acids and bases principles in Ag(I) coordination.

Purpose of the Study:

  • To report the first silsesquioxane-protected superatomic silver nanocluster, Ag40.
  • To introduce an adaptive multipath synthesis method to overcome limitations in Ag(I) coordination chemistry.
  • To explore the synthetic routes and assembly pathways of the nanocluster.

Main Methods:

  • Single-crystal X-ray diffraction to determine the kernel-shell architecture of Ag40.
  • Synthetic methodology studies exploring three routes (in situ, pre-synthesis, hierarchical) for accessing macrocyclic Ph4Si4O8 ligands.
  • Mass spectrometry to investigate ligand transformation and nanocluster assembly pathways.

Main Results:

  • The first silsesquioxane-protected superatomic silver nanocluster, [Ag40(Ph4Si4O8)6(tBuC≡C)8] (Ag40), was synthesized.
  • A kernel-shell structure with an Ag16(8+) kernel and a [Ag24(Ph4Si4O8)6] cage was revealed.
  • The hierarchical synthesis approach improved reproducibility and crystal growth efficiency.
  • Ag40 exhibits superatomic 1D→1P transition-dominated red phosphorescent emission.

Conclusions:

  • The study establishes a new paradigm for silica-supported superatom synthesis.
  • It advances the field of hard-base-protected coinage metal nanoclusters.
  • The findings highlight the critical role of dynamic silsesquioxane transformations in capturing ultrasmall silver kernels.