Date of Award
Spring 3-6-2024
Degree Type
Dissertation/Thesis
Degree Name
Masters of Science in Chemical Science
Department
Department of Chemistry and Biochemistry
Committee Chair/First Advisor
Dr. Daniela Tapu
Second Advisor
Dr. Graham Collier
Third Advisor
Dr. Bharat Baruah
Abstract
Understanding structure-property relationships of π-conjugated chromophores based on peripheral functionalization is important for the continued development of various organic electronic applications. 1,4-Dihydropyrrolo[3,2-b]pyrroles (DHPPs) are synthetically simple chromophores with tailorable optical and electrochemical properties based on the functionalities of the starting materials. The overarching goal of this thesis is to understand how peripheral functionalization strategies enable distinctly different optical and electrochemical properties that may be useful for various applications. Motivated by the synthetic simplicity and tunability of DHPPs, molecules with varying design motifs were synthesized to exhibit how functionality influences optical and electrochemical properties. First, two molecules with varying degrees of electron-donating ability were predicted by calculations to possess distinctly different optical properties as oxidized chromophores. The molecules were synthesized and investigated to elucidate how the subtle structural changes affect the optoelectronic properties and these changes were measured via UV-vis absorbance spectroscopy, cyclic voltammetry (CV), and differential pulse voltammetry (DPV). Investigations reveal the ability to manipulate the absorbance spectrum of neutral and oxidized species to obtain control of the radical cation. Next, pyridine-functionalized DHPPs were synthesized and the position of the nitrogen atom in the aromatic ring was found to influence the optoelectronic properties. These new DHPPs were also shown to participate in Pd-catalyzed cross-coupling reactions and enabled characterization of π-extended DHPPs. Ultimately, my findings demonstrate the ability to exploit the simple and tailorable DHPP synthesis to manipulate optical and redox activity. This work is important for the continued development of strategies to tailor optoelectronic properties of synthetically-simple DHPP molecules and eventual incorporation into organic electronic devices.
Comments
National Science Foundation (Award No. 2203340)