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Light-Activated Intercluster Conversion of an Atomically Precise Silver Nanocluster.

Arijit Jana1, Madhuri Jash1, Ajay Kumar Poonia2

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Summary
This summary is machine-generated.

Noble metal nanoclusters featuring carboranes exhibit unique properties. Researchers synthesized a high-nuclearity silver nanocluster (Ag42) that transforms into a smaller cluster (Ag14) upon light irradiation, revealing new insights into cluster dynamics.

Keywords:
carboranesintercluster conversionluminescencenear-infrared emissionsilver nanoclustersultrafast electron dynamics

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Area of Science:

  • Materials Science: Synthesis and characterization of novel noble metal nanoclusters.
  • Nanotechnology: Exploration of carborane-protected silver nanoclusters with unique structures.
  • Physical Chemistry: Investigation of light-induced transformations and photophysical properties.

Background:

  • Carboranes, 12-vertex boron-carbon frameworks, are increasingly used as protecting ligands for noble metal nanoclusters.
  • These nanoclusters possess distinct physicochemical properties due to their unique structures and ligand shells.
  • Understanding the synthesis and transformation pathways of these advanced nanomaterials is crucial for their applications.

Purpose of the Study:

  • To synthesize and characterize a novel, high-nuclearity silver nanocluster protected by carborane and triphenylphosphine ligands.
  • To investigate the structural transformation of the synthesized silver nanocluster upon light irradiation.
  • To elucidate the mechanism of light-induced intercluster conversion and the photophysical properties of the resulting nanoclusters.

Main Methods:

  • Synthesis of [Ag42(CBDT)15(TPP)4]2- (Ag42) from [Ag18H16(TPP)10]2+ via ligand-exchange induced structural transformation.
  • Characterization using UV-vis absorption spectroscopy, mass spectrometry, TEM, XPS, IR, and NMR spectroscopy.
  • Investigation of light-induced transformation using time-dependent mass spectrometry and single crystal X-ray diffraction of the product (Ag14).

Main Results:

  • Successful synthesis of Ag42, the highest nuclearity carborane-protected silver nanocluster reported to date.
  • Light irradiation of Ag42 solutions induced a structural conversion to a smaller Ag14 nanocluster with a core-shell structure.
  • Time-dependent studies revealed intermediate clusters during the light-activated conversion, explained by DFT calculations.
  • Ag42 exhibited phosphorescence (980 nm), while Ag14 showed fluorescence (626 nm), with distinct carrier dynamics observed.

Conclusions:

  • The study demonstrates a novel light-activated transformation pathway for carborane-protected silver nanoclusters.
  • The findings provide fundamental insights into the structural dynamics and photophysical properties of high-nuclearity silver nanoclusters.
  • This work opens avenues for designing and controlling nanocluster structures and functions through external stimuli like light.