Glyme-synthesized nanomaterials
Date
2021
Authors
Armstrong, James, author
Ackerson, Christopher J., advisor
Prieto, Amy, committee member
Kennan, Alan, committee member
Basaraba, Randall, committee member
Journal Title
Journal ISSN
Volume Title
Abstract
Nanomaterials include materials with at least one dimension in the nanometer range. These materials include nanoparticles, quantum dots, thin films, self-assembled materials, supramolecular materials and more. Nanoscience is an intriguing field for cutting edge research for energy, biology, medicine, optical and other applications. Coinage-metal (Au, Ag, Cu) nanomaterials are particularly of interest for the stability of nanoparticles synthesized with these metals. These metals can also be utilized to produce supramolecular assemblies, e.g. Hydrogels. In particular, this dissertation will cover four projects involving coinage metal nanomaterials. Chapter 2 discusses the ligand-exchange of a gold-thiolate nanocluster synthesized in diglyme, while chapters 3-5 investigate a unique supramolecular assembly of coinage-metal thiolates using glymes as antisolvent. Chapter 3 explores the underlying makeup of these amorphous assemblies, while chapters 4 and 5 investigate the application of this supramolecular assembly for additive manufacturing applications and antimicrobial applications, respectively. All of these products are linked through the synthesis and characterization of nanomaterials, which require the use of glymes (1,2-dme, diglyme, triglyme, etc.) as a necessary synthetic solvent or antisolvent. Nanoclusters are small, atomically precise nanoparticles with a metal core and a passivating layer of organic ligands. Coinage metal nanoclusters are studied for their stability, especially gold nanoclusters, allowing for long-term studies of properties and applications, as well as post-synthetic modifications. Precise control over ligand shell composition, particularly of mixed ligand layers is desired for control over nanocluster functionality. Supramolecular materials build bulk properties through noncovalent interactions. Self-assembled supramolecular materials utilize small molecules which assemble into larger secondary and tertiary structures. These materials are of interest for a broad range of applications like additive manufacturing and biological applications. The motivation behind this work was to explore nanomaterials which results from a glyme based synthesis. Gold nanocluster synthesis in diglyme is found to produce a stable gold-thiolate nanocluster with a single glyme ligand. The precision of a single-unique ligand could lead to further enhancements in nanocluster functionality in the future. Addition of glyme to a coinage-metal thiolate solution results in the rapid precipitation of a rigid supramolecular assembly. The resultant metallogel exhibits properties unique from similar materials without the use of glyme in synthesis. The metallogel is composed of oligomers reminiscent of nanoparticle precursors; as such, metallogel-nanoparticle composites are readily synthesized.