Development of Alkene Difunctionalization As A Versatile Method For Polymerization
Restricted (Penn State Only)
- Author:
- Katzbaer, Julia
- Graduate Program:
- Chemistry
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- July 20, 2023
- Committee Members:
- Ramesh Giri, Co-Chair & Dissertation Advisor
Elizabeth Elacqua, Co-Chair & Dissertation Advisor
Eric Nacsa, Major Field Member
Raymond Schaak, Major Field Member
Philip Bevilacqua, Program Head/Chair
Enrique Gomez, Outside Unit & Field Member - Keywords:
- Polymerization
Difunctionalization
Ni-catalyzed - Abstract:
- Polymer materials are an essential component of the global architecture of modern society. As such, extensive efforts continue toward developing new methods of polymerization and accessing materials with diverse and valuable properties. Herein, this dissertation describes the adaptation of nickel-catalyzed alkene diarylation for polymerization, providing access to a new class of polymer: poly(arylene -(aryl)ethylene)s. Thorough method optimization (that let to complete suppression of the competitive anionic polymerization) resulted in polymers exhibiting a wide range of molecular weights and dispersities. Characterization of the product materials, which exhibit structural similarities to both polystyrene and poly(phenylene methylene), revealed thermal behavior reminiscent of both materials and photophysical properties akin to the homoconjugation observed in poly(phenylene(methylene))s. Accordingly, this new method was then expanded to incorporate other desirable polyaromatic hydrocarbon and heteroatom co-monomers, as well as to study the tolerance of the method to bulky boronic ester co-monomers. The resulting studies expand the substrate scope and introduce components known to exhibit valuable photophysical properties into the polymer. Upon introduction of these pendant species, their photophysical behaviors, such as J-aggregation and excimer formation, appear to be promoted by inherent proximity resulting from the polymer scaffold. Thus, the work described in this dissertation emphasizes the advancement of polymerization methodology and the access provided therein to new materials with added functionality.