Author ORCID Identifier
Year of Publication
Doctor of Philosophy (PhD)
Arts and Sciences
Dr. Chad Risko
Though organic semiconductors have illustrated potential as industry-relevant materials for electronics applications, there are few guidelines that can take one from molecular design to functional materials. This limitation is, in part, due to incomplete understanding as to how the atomic-scale construction of the π-conjugated molecules that comprise the organic semiconductors determines the nature and strength of both the noncovalent intramolecular interactions that govern molecular conformation and noncovalent intermolecular interactions that regulate the energetic preference for solid-state packing. Hence, there remain several fundamental questions that need to be resolved in order to design organic semiconductors from a priori knowledge, including: What is the relevance of the relatively weak noncovalent intramolecular interactions on determining molecular structure, are current hypotheses put forward as to important interactions valid, and how does chemical substitution as various positions along the π-conjugated backbone impact these interactions? How do the intermolecular noncovalent interactions regulate solid-state packing, are there features of the molecular structure – e.g. the π-conjugated backbone, heteroatoms, or pendent alkyl chains – that play a more important role? What connections can be made between the structures/properties of the π-conjugated molecules and the resulting organic semiconductors?
In this dissertation, Chapter 1 provides an introductory discussion of these questions and a brief review of previous studies. Chapter 2 details the computational approaches that were implemented throughout the course of the thesis work. Chapter 3 describes the investigation of a series of pyrene-acene molecules to illustrate the importance of choosing the right molecular structure in π-conjugated chromophores. In Chapter 4, S...F noncovalent intramolecular interactions are systematically investigated in two separate cases to highlight the varied impact that these interactions can have on molecular and solid-state packing structures. Chapter 5 describes the investigation of an oscillatory crystal packing structure observed for a series of oligothiophenes that follow the odd-even carbon-atom counts of the pendant alkyl chains. In Chapter 6, the polymorphism of functionalized pentacene molecules is studied to reveal how seemingly simple atomic substitutions can drastically alter solid-state packing. To systematically address the aforementioned fundamental questions, Chapter 7 describes the construction and application of a database of crystalline molecular organic semiconductors. Finally, perspectives regarding future research are provided in Chapter 8.
Digital Object Identifier (DOI)
Portions of the work presented in this dissertation were supported by the National Science Foundation (NSF) Designing Materials to Revolutionize and Engineer our Future (DMREF) program in the Division of Materials Research (award number DMR-1627428, October 1, 2016 - June 30, 2020).
Ai, Qianxiang, "TOWARDS THE RATIONAL DESIGN OF ORGANIC SEMICONDUCTORS THROUGH COMPUTATIONAL APPROACHES" (2020). Theses and Dissertations--Chemistry. 126.