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

Ananya Baksi, Megalamane Siddaramappa Bootharaju, Pratap K. Chhotaray, Papri Chakraborty, Biswajit Mondal, Shridevi Bhat, Ramesh L. Gardas, Thalappil Pradeep

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8 Scopus citations


Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till 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 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 towards excess ligand com-pared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mech-anism of these silver clusters and nanoparticles. Effect of dissolved oxygen in the degradation process was studied in de-tail and 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.
Original languageEnglish (US)
Pages (from-to)26483-26492
Number of pages10
JournalThe Journal of Physical Chemistry C
Issue number47
StatePublished - Nov 16 2017
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: A.B. and T.P. thank the Department of Science and Technology, Government of India for continuous support our of research program on nanomaterials. A.B. thanks Indian Institute of Technology Madras for fellowship.


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