Strategies for the Total Synthesis of Inorganic Nanostructures

Open Access
Buck, Matthew Robert
Graduate Program:
Doctor of Philosophy
Document Type:
Date of Defense:
May 22, 2013
Committee Members:
  • Raymond Edward Schaak, Dissertation Advisor
  • Thomas E Mallouk, Committee Member
  • Christine Dolan Keating, Committee Member
  • Michael Anthony Hickner, Committee Member
  • materials
  • synthesis
  • nanoscience
  • hybrid
  • nanoparticles
  • colloids
Colloidal nanochemistry is a maturing branch of chemistry that is concerned with the liquid-phase synthesis, manipulation, and properties of nanometer-scale inorganic building blocks that have prescribed sizes, shapes, compositions, and surfaces. Efforts to construct functional materials from such building blocks represent a promising alternative approach to the conventional miniaturization techniques developed for modern microelectronics. Hence, the individual inorganic building blocks can be considered as tailorable fundamental units, from which new materials with designer properties can be constructed. Colloidal nanochemistry is advantageous in this endeavor, because it has the potential to enable exquisite morphological control over individual nanocrystallites, and to permit inexpensive, high-throughput, liquid-phase processing into hierarchical nanostructures. To address the demand for complex, next-generation nanomaterials with rigorously controlled architectures and interfaces using colloidal nanochemistry, synthetic innovations must be developed. In this dissertation, the total synthesis framework used by organic chemists to prepare complex molecules has been used as a source of inspiration for approaching the colloidal synthesis of such multi-component inorganic nanostructures. Within this framework, we emphasize the importance and utility of single-component crystalline nanoparticles, which can be treated as synthons that can be chemically transformed into more complex derivatives. Furthermore, those transformations can be categorized into classes of reactions that are related to those used in the synthesis of organic molecules. We also demonstrate that concepts used in molecular synthesis – including site-selectivity, regio- and chemoselectivity, orthogonal reactivity, coupling reactions, and protection-deprotection strategies – can be applied to colloidal nanochemistry. Collectively, this synthetic framework represents an emerging paradigm in the synthesis of complex inorganic nanostructures: applying the guiding principles that underpin the multi-step “total synthesis” framework used to produce complex organic molecules and natural products to the stepwise construction of complex multi-component nanostructures.