Dissertations, Theses, and Capstone Projects

Date of Degree

9-2016

Document Type

Dissertation

Degree Name

Ph.D.

Program

Chemistry

Advisor

Charles Michael Drain

Committee Members

Hiroshi Matsui

Yuhang Ren

Michele Vittadello

Neepa Maitra

Subject Categories

Materials Chemistry | Other Chemistry | Physical Chemistry

Keywords

Nanotechnology, Supramolecular Chemistry, Self Assembly, Porphyrins, Phthalocyanines, Photonics

Abstract

Porphyrins (Pors) and their many cousins, including phthalocyanines (Pcs), corroles (Cors), subphthalocyanines (SubPcs), porphyrazines (Pzs), and naphthalocyanines (NPcs), play amazingly diverse roles in biological and non-biological systems because of their unique and tunable physical and chemical properties. These compounds, collectively known as porphyrinoids, can be employed in any number of functional devices that have the potential to address the challenges of modern society. Their incorporation into such devices, however, depends on many structural factors that must be well understood and carefully controlled in order to achieve the desired behavior. Self-assembly and self-organization are key processes for developing these new technologies, as they will allow for inexpensive, efficient, and scalable designs. The overall goal of this dissertation is to elucidate and ultimately control the interplay between the hierarchical structure and the photophysical properties of these kinds of systems. This includes several case studies concerning the design and spectroscopic analysis of supramolecular systems formed through simple, scalable synthetic methods. We also present detailed experimental and computational studies on some porphyrin and phthalocyanine compounds that provide evidence for fundamental changes in their molecular structure. In addition to their impact on the photophysics, these changes also have implications for the organization of these molecules into higher order materials and devices. It is our hope that these findings will help to drive chemists and engineers to look more closely at every level of hierarchical structure in the search for the next generation of advanced materials.

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