Reactivity of Monolayer Protected Silver Clusters toward Excess Ligand: A Calorimetric Study

Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. To date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in the presence of excess ligand, GSH, using isothermal titration calorimetry (ITC). We have studied Ag₁₁(SG)₇ and Ag₃₂(SG)₁₉ clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity toward excess ligand compared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mechanism of these silver clusters and nanoparticles. The effect of dissolved oxygen in the degradation process was studied in detail, and it was found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined, including density, speed of sound, isentropic compressibility, and coefficient of thermal expansion.