Beyond Traditional Superatom Ligands and Cores
By: Evan Ambrose Doud
Publisher: [publisher not identified]
Published: 2020
Place of publication: [New York, N.Y.?]
Language: eng
Description: This dissertation summarizes my research in the Roy group on the development, synthesis, and study of new N-heterocyclic carbene (NHC) based ligands and nickel phsophinidene core compositions of molecular clusters, also known as superatoms. Chapter 1 introduces superatoms as atomically precise and discreet building blocks for use in the design and synthesis of novel materials. A brief history as well as selected synthetic strategies of superatoms will be introduced. The relevant materials properties of superatoms as well as their dependence on core composition and ligand structure will be discussed. Next, the use of superatoms with specialized or functionalizable ligands to synthesize new materials will be demonstrated. This chapter details the importance of the superatom ligands and core composition is the foundation that the subsequent chapters builds upon in developing these two areas. Chapter 2 introduces a functionalized NHC as a potential superatom ligand. While not necessary for all superatom ligands, ligands that enable electronic access to the superatom core are attractive.

In this chapter, the conductance of potential NHC based ligands are probed through the scanning tunneling microscope-based break-junction (STM-BJ) method. A novel method of forming single molecule junctions in situ was used and these ligands are found to display a length dependent conductance with strong coupling to the Au electrode, confirming their potential use as ligands for superatoms. Chapter 3 describes the nature of the NHC–M bond in self-assembled monolayers (SAMs) on a Au(111) surface using high-resolution spectroscopy and theoretical calculations. This study was performed as a result of challenges and questions encountered during the work of Chapter 2. The results obtained from this study explore an important structure-function relationship of NHC ligands and have broader impact in materials chemistry beyond superatoms. Chapter 4 explores the synthesis of superatoms with NHC ligands beyond simple imidazolium-based NHCs. This chapter describes the two primary synthetic techniques used and the synthesis of NHC-ligated superatoms.

This work is also ongoing and characterization is limited to crude single crystal X-ray diffraction structures and select NMRs. Finally, Chapter 5 details the use of uncommon organocyclophosphine reagents to synthesis novel nickel-phosphinidene molecular clusters, a potential new superatom. In this chapter the synthesis of a family of nickel-phosphinidene molecular clusters is described and studied. A potential application of these molecular clusters is explored through the thermolytic conversion to the industrially relevant Ni2P.
Notes: Department: Chemistry.

Thesis advisor: Xavier Sylvain Roy.

Thesis (Ph.D.)--Columbia University, 2020.