Type
Text
Type
Dissertation
Advisor
GOROFF, NANCY | MAYR, ANDREAS | GRILLS, DAVID C | WONG, STANISLAUS | LIKHAREV, KONSTANTIN.
Date
2015-08-01
Keywords
Inorganic chemistry
Department
Department of Chemistry.
Language
en_US
Source
This work is sponsored by the Stony Brook University Graduate School in compliance with the requirements for completion of degree.
Identifier
http://hdl.handle.net/11401/77152
Publisher
The Graduate School, Stony Brook University: Stony Brook, NY.
Format
application/pdf
Abstract
Shape-persistent molecular cages with significant internal cavities are very attractive synthetic targets owing to their multifarious applications. We have focused on the design and synthesis of molecular cages that may be used as structural components in single-electron transistors (SETs) designed by K. K. Likharev. This application requires not only shape-persistent cages, but also stable and selectively functionalizable structures with cavities that can host the SET's conducting island. In this vein, we have designed two molecular cages, a triangular prism (1) and rhomboid prism (2). Both cages consist of oligo-phenyleneethynylene edges and fac-[ReL(CO)3(phen')] corner units, where phen' is a 1,10-phenanthroline derivative with coplanar edge substituents at the 4 and 7 positions and L indicates the coordination site for the vertical-edge. Synthesis of cages 1 and 2 are intended to be achieved by via step-wise synthesis. Most often molecular cages are obtained from suitable building blocks in a single step by self-assembly. Although self-assembly is both a convenient and productive procedure, it is limited to producing structures with a high degree of symmetry. Because we require stable structures that can be functionalized at various specified positions, we elected to use step-wise rather than self-assembly in their construction. This work addresses the progress made in the construction of 1 and 2, specifically, the synthesis of a triangular-shaped face and the attempted synthesis of a diamond-shaped face. In addition, our efforts to establish optimal reactions conditions for the connection of two halfprisms by testing Sonogashira cross-coupling reactions of [Re(C≡ CR)(CO)3(N^N)] complexes, where N^N is a N,N'-dimethylpiperazine or 1,10-phenanthroline derivative, will be discussed. Finally, in collaboration with Etsuko Fujita and David Grills we have explored redox, optical, and photophysical properties of a series of [ReBr(CO)3(phen')] complexes, which are known for their attractive photophysical and photochemical properties. | 304 pages
Recommended Citation
St. Fleur, Natalie, "Towards the Step-wise Synthesis of Molecular Cages: Potential Components in Single-Electron Transistors" (2015). Stony Brook Theses and Dissertations Collection, 2006-2020 (closed to submissions). 2988.
https://commons.library.stonybrook.edu/stony-brook-theses-and-dissertations-collection/2988