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Divergent Transformation Pathways from a Common Au25 Intermediate: The Effect of "Positional Isomerism"
Nida Nahan Eyyakkandy1, Seiji Yamazoe2, Sukhendu Mandal1
1School of Chemistry, Indian Institute of Science Education and Research, Thiruvananthapuram, Kerala 695551, India.
The Journal of Physical Chemistry Letters
|December 17, 2025
Summary
Ligand substituent position influences metal nanocluster transformation. Subtle differences in methylbenzenethiols guide the synthesis of gold nanoclusters (Au NCs) via ligand exchange-induced structural transformation (LEIST).
Area of Science:
- Nanoscience and Nanotechnology
- Materials Chemistry
- Surface Chemistry
Background:
- Metal nanoclusters (NCs) offer atomic-scale precision and tunable properties.
- Controlled synthesis of NCs remains a significant challenge in nanoscience.
- Ligand exchange-induced structural transformation (LEIST) is a key strategy for understanding NC dynamics.
Purpose of the Study:
- To investigate the impact of ligand substituent position on the structural transformation of gold nanoclusters.
- To explore how positional isomers of methylbenzenethiols influence the synthesis of [Au23(CHT)16]-.
- To provide insights into the rational design of gold nanoclusters through ligand control.
Main Methods:
- Ligand exchange-induced structural transformation (LEIST) using positional isomers of methylbenzenethiols (2-MBT, 3-MBT, 4-MBT).
- Time-dependent mass spectrometry for tracking transformations.
- Nuclear Magnetic Resonance (NMR) spectroscopy for structural elucidation.
- Detailed structural analysis of nanocluster intermediates and products.
Main Results:
- A common intermediate was identified during the transformation process.
- Positional isomers of methylbenzenethiols led to divergent product pathways.
- The position of the ligand substituent significantly influenced the structural growth pathways of the gold nanoclusters.
Conclusions:
- Ligand positional isomerism acts as a critical control factor in the synthesis of gold nanoclusters.
- Understanding these effects enables more precise and desired synthesis of specific Au NC structures.
- This study provides fundamental insights for the rational design of metal nanoclusters.
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