Synthesis of Helically Chiral and Heteroatom-Doped Nanographenes and PAH Electronic Applications
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Authors
Malone, Ryan Joseph
Issue Date
2023
Type
Dissertation
Language
Keywords
Alkyne Benzannulation , Graphene Nanoribbons , Helicenes , Heteroatom Doping , Nanographenes , Organic Electronics
Alternative Title
Abstract
Nanographenes and larger polycyclic aromatic hydrocarbons such as graphene nanoribbons are of great interest in the design of organic electronics due to their absorbance, fluorescence, and semiconducting properties. Through creative synthetic design following a broad range of bottom-up strategies, these properties can be tuned to better suit the molecules’ practical applications. Chief among these strategies, as they pertain to this work, are heteroatom-doping and changes in the size and shape of the PAH backbone to introduce helical chirality. Through functionalization of the cove and fjord regions of laterally expanded [4]- and hetero[5]helicenes, respectively, we synthesized a range of chiral compounds with barriers to enantiomerization far exceeding those of [4]- and [5]helicenes, allowing us to easily separate and study the enantiomers’ optical properties. We also explored heteroatom doping with sulfur, oxygen, and nitrogen, as a means of tuning the optical and electronic properties of nanographene backbones. Lastly, we demonstrated the practical application of our group’s compounds by incorporating them into electronic devices. Peropyrene was used as the cathodic intercalation matrix in the first zinc ion battery to employ nanographenes as one of the electrodes, and our graphene nanoribbons were used to make the first solar cells that use graphene nanoribbons as the active layer for absorption across a broad range of the solar spectrum.