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Predicting ligand removal energetics in thiolate-protected nanoclusters from molecular complexes
Julia McKay1, Michael J Cowan, Cristian A Morales-Rivera
1Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA. gmpourmp@pitt.edu.
Nanoscale
|January 15, 2021
Summary
Ligand removal from thiolate-protected metal nanoclusters (TPNCs) is crucial for catalysis. This study uses DFT to correlate metal-sulfur and sulfur-ligand bond strengths, enabling prediction of ligand removal energies for catalyst design.
Area of Science:
- Materials Science
- Computational Chemistry
- Catalysis
Background:
- Thiolate-protected metal nanoclusters (TPNCs) are stable, precisely structured materials with significant catalytic potential.
- Ligand removal is essential for generating active sites in TPNC catalysts, but the underlying mechanisms and influencing factors are not fully understood.
Purpose of the Study:
- To investigate the energetic factors governing metal-sulfur and sulfur-ligand bond dissociation in metal-thiolate systems.
- To develop a predictive model for ligand removal energetics in TPNCs based on molecular complex calculations.
Main Methods:
- Density Functional Theory (DFT) calculations were employed.
- 66 metal-thiolate molecular complexes (Ag, Au, Cu with 22 ligands) were analyzed.
- The methodology was extended to a relevant [M25(SR)18]- TPNC model.
Main Results:
- A strong correlation was found between metal-sulfur and sulfur-ligand bond dissociation energies, linked to metal atomic ionization potentials.
- This correlation holds true for both molecular complexes and TPNCs.
- A predictive model was successfully developed using molecular complex data.
Conclusions:
- The study provides a unified understanding of ligand removal energetics in TPNCs.
- The developed model offers an accelerated approach for predicting ligand removal energies.
- This aids in the rational design of novel TPNC catalysts with tailored properties.
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