Using atomically precise clusters to model materials
Creators: Beecher, Alexander Nathaniel
Publisher: name: Columbia University
Year: 2016
Subjects: Cadmium selenide
Nanostructured materials
Oligomers
Oligomers--Synthesis
Microclusters
Chemistry
Materials science
Chemistry, Inorganic

description: Using two different model systems, this thesis considers the old, but fascinating question: how do atoms or particles possessing a particular set of individual characteristics combine to form assemblies with quite distinct, ensemble characteristics, and how do those characteristics evolve as a function of the size of the assembly? For the last thirty years, numerous experiments studying the emergence of collective material properties have focused on a class of semiconducting, colloidal nanocrystals commonly known as quantum dots, which are notable for the size-dependence of their optical properties. Despite years of effort, even the most uniform quantum dot samples possess some heterogeneity in size, shape, and composition, which has prevented complete structure determination and hindered understanding of structure-property relationships. Chapter 1 of this thesis presents an approach to overcoming this challenge and reports the synthesis of a set of four, new, atomically precise cadmium selenide nanocrystal samples, which we call CdSe(350 nm), CdSe(380 nm), CdSe(408 nm), and CdSe(435 nm) after their lowest energy absorption features. We determine their structures and formulas through a combination of single crystal and powder X-ray diffraction measurements, elemental analysis, and spectroscopy. We also describe the optical properties of these samples and their sensitivity to ligand coverage, compare them to other previously reported cadmium selenide nanomaterials, and discuss ongoing experiments.
      Because CdSe(350 nm), CdSe(380 nm), CdSe(408 nm), and CdSe(435 nm) are atomically precise, they allow us to correlate specific structural features with material properties, which is the focus Chapter 2. Here we present a series of Raman scattering experiments designed to probe the evolution of vibrational structure with size. We find that the Cd-Se stretching region of the Raman spectra exhibits two peaks, which are assigned to primarily surface-derived and interior-derived atomic motions using density functional theory calculations. By performing variable temperature measurements, we discover that the smallest sample, CdSe(350 nm), exhibits behavior that can be well-described using a model developed for small molecules while the vibrations of the largest measured cluster, CdSe(408 nm), are better described by a model developed for bulk materials. This observation is evidence that the transition to a more bulk-like vibrational structure occurs relatively rapidly when cadmium selenide materials are approximately 2 nm in size.
      The emergence of collective material properties is also the subject of Chapter 3, but the topic is approached from a different perspective. Instead of focusing on a series of atomically precise clusters that differ in size, Chapter 3 presents a series of molecules composed of atomically precise clusters. We prepare octahedral hexaruthenium carbonyl clusters, [Ru₆C(CO)₁₆]²⁻, and use them as building blocks to assemble oligomers linked by single metal atom bridges. We synthesize and structurally characterize a set of compounds varying in length (from monomer to trimer) and linker atom identity (cadmium and mercury) and study the effect on electronic structure using infrared and UV-Visible absorption spectroscopies and density functional theory calculations. With increasing oligomer length, the UV-Vis absorption profile changes and shifts to lower energy, which we attribute in part to the development of coupling between neighboring clusters. Our calculations show that the infinite polymer composed of [Ru₆C(CO)₁₆]²⁻ linked by Hg²⁺ would be a one-dimensional semiconductor with a 1.5 eV direct band-gap.
      More detailed abstracts can be found at the beginning of each chapter.