(318d) Rationalizing Stability and Doping of Atomically Precise Ligand-Protected Metal Nanoclusters

Ligand-protected colloidal nanoclusters of precise size, shape, and composition have attracted interest as model systems in applications from medical imaging to catalysis. Though several thiolate-protected metal clusters have been determined with atomic precision, relatively little is understood of what underlying physics result in their remarkable stability and resultant colloidal monodispersity. Herein we highlight our work [1-4] proposing a new thermodynamic stability theory based on cluster interfacial energetics. Additionally, we extend this theory to rationalize heterometal doping energetics, concentrations, and preferred dopant sites within several bimetallic gold-based nanoclusters. Beyond this new theory, we tie experimental doping observations to the energetics of reactions between nanoclusters and solution-phase precursor complexes. Overall, we present work that further develops understanding of stability and doping atomically-precise metal nanoclusters that can be used for predictions of synthesizable nanoclusters for targeted applications.

[1] M. G. Taylor, G. Mpourmpakis, Thermodynamic Stability of Ligand-Protected Metal Nanoclusters. Nature Communications 8, 15988 (2017).

[2] Q. Li et al., Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping. Journal of the American Chemical Society 139, 17779-17782 (2017).

[3] Q. Li et al., Molecular “surgery” on a 23-gold-atom nanoparticle. Science Advances 21, 1-8 (2017).

[4] Q. Li et al., Site-selective substitution of gold atoms in the Au₂₄(SR)₂₀ nanocluster by silver. Journal of Colloid and Interface Science 505, 1202-1207 (2017).