The dynamic nature of ligand layers on gold nanoclusters
Date
2020
Authors
Hosier, Christopher Allen, author
Ackerson, Christopher J., advisor
Kennan, Alan J., committee member
Henry, Chuck, committee member
Kipper, Matthew, committee member
Journal Title
Journal ISSN
Volume Title
Abstract
Gold nanoclusters have been heavily investigated over the last few decades for their potential use in sensing, imaging, energy conversion, and catalytic applications. The development of methodology that allows for controlled functionalization of the surface ligand layer in these compounds is of particular interest due to the role of ligands in determining a large number of cluster properties. One of the fundamental ways of tailoring the ligand layer is the use of ligand exchange reactions. Despite the synthetic utility that ligand exchange reactions afford, a significant number of unanswered challenges currently limits the scope and control that can be obtained with these reactions. While a large variety of ligand types have been used to protect nanocluster surfaces, the majority of reported ligand exchange reactions revolve around chalcogenate-for-chalcogenate exchange. Site-selectivity in these reactions is limited to kinetic phenomenon, and the role of intercluster exchange largely remains a mystery. Additionally, recent works suggest that changes in ligand orientation can impact bulk material properties. In this thesis, we seek to address these challenges by reporting new exchange methodology, probing the evolution of exchanged ligand layers over time, investigating the stability of ligand layers in reaction conditions, and exploring the impact of ligand orientation on nanocluster behavior and reactivity. By addressing these questions and challenges, we seek to move closer to the goal of developing methodology that can be easily and reliably used to tailor gold nanoclusters for directed applications.