Title: Cove-Edge Graphene Nanoribbon Semiconductors
Description: This dissertation presents research conducted on the structure-property relationships of cove-edge graphene nanoribbon (GNR) semiconductors from the scale of molecular conformation to device performance. The ribbons described here are made derived from perylene-3,4,9,10-tetracarboxylic acid diimide (PDI) and adopt a helical conformation so we call them helical PDI (hPDI). They are n-type semiconductors with exceptional performance in field-effect transistors (FETs), organic photovoltaics (OPVs), narrowband photodetectors, and electron transporting materials in perovskite solar cells. In this work, reaction chemistry is used to design and synthesize new derivatives of hPDI to shine light on their molecular, bulk, and device properties. The first chapter concerns the incorporation of hPDI into alternating donor- acceptor (D-A) macromolecules to create materials with internal charge transfer (CT). Computational and spectroscopic techniques, including femtosecond transient absorption spectroscopy (fsTA), are used to probe the CT character of these materials.

A large dihedral angle between donor and acceptor portions limits orbital overlap, leading to lowest energy excited state with HOMO localized on the donor and LUMO localized on the acceptor. Notably, internal CT improves the OPV performance of these oligomers over their parent hPDI, while analogous macromolecules without internal CT exhibit reduced OPV performance. Chapter 2 details a method for side chain engineering of hPDI by installing the side chain in the final step of the synthesis, rather than the first. The aromatic core of hPDI is built up with esters, rather than imides, appending the edges of the ribbons. The ester-appended ribbons are readily transformed into a late-stage intermediate for divergent installation of any desired side chains, including those that pose synthetic challenges when they are introduced into the parent PDI from the beginning. These side chains have a profound effect on the optical, thermal, and charge transport properties of hPDI in the solid state. This strategy of introducing imide side-chains into PDI-based materials in the final step can be generalized to other systems.

Chapter 3 demonstrates a method for controlling the conformation of cove-edge GNRs by changing the chemical substitution pattern at their edges. All-sp2 substituents that lock adjacent edge positions into a ring rigidify the aromatic core of these ribbons. When substituents at adjacent edge positions are no longer locked into a ring, the aromatic core becomes flexible. Modulating this flexibility dictates how these ribbons contort to accommodate their cove-edges, with rigid cores contorting into chiral helixes, and flexible cores contorting into a butterfly conformation. This may point the way forward for the use of GNRs in applications that rely on precise control of molecular conformation.