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Insights into Racemization of Metal Nanoclusters and Strategic Spontaneous Resolution.

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  • 1College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China.

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|February 23, 2026
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Summary

Chiral metal nanoclusters often form racemic mixtures. This study reveals that reducing intermolecular interactions between enantiomers in the crystal unit cell enables spontaneous chiral resolution, yielding homochiral crystals.

Keywords:
chiralitycluster compoundsligand engineeringself-assemblyspontaneous resolution

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Area of Science:

  • Materials Science
  • Supramolecular Chemistry
  • Nanotechnology

Background:

  • Chiral metal nanoclusters are crucial for advanced applications.
  • Enantiomers of these nanoclusters typically crystallize as racemic mixtures, hindering their use.
  • Understanding racemization mechanisms is key to achieving enantiopure materials.

Purpose of the Study:

  • To elucidate the mechanism of racemization in chiral metal nanoclusters.
  • To propose a rational strategy for achieving spontaneous chiral resolution.
  • To demonstrate methods for obtaining enantiopure metal nanoclusters.

Main Methods:

  • Investigated intermolecular interactions (e.g., C-H···F, C-H···π) stabilizing racemic assemblies.
  • Modified ligand substituents (fluorine removal, thiophene incorporation) to disrupt these interactions.
  • Utilized mirror-image circular dichroism spectroscopy to confirm enantiopurity.

Main Results:

  • Racemic cluster crystallization is driven by intermolecular interactions between opposite enantiomers.
  • Eliminating or weakening these interactions leads to spontaneous resolution into homochiral crystals.
  • Demonstrated resolution in Cu25 and Cu4 nanocluster systems by ligand modification.

Conclusions:

  • Intermolecular interactions critically govern racemate formation in chiral metal nanoclusters.
  • Strategies targeting these interactions enable rational design for spontaneous chiral resolution.
  • This work provides a pathway to enantiopure metal nanoclusters for chiral applications.