Chiral and Achiral Nanographenes: Tuning the Properties via Molecular Design
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Authors
Magiera, Kelsie
Issue Date
2022
Type
Dissertation
Language
Keywords
Alternative Title
Abstract
Methodology towards the enantioselective alkyne benzannulation to afford both chiral peropyrene and chiral picene were studied. A variety of Lewis acids were screen for the racemic alkyne benzannulation reaction. Both chiral Lewis acids and chiral Brønsted acids were investigated for the promotion of the enantioenriched two-fold alkyne benzannulation. Enantioselective syntheses of nanographenes (NGs) including chiral picene and chiral peropyrene provide an excellent opportunity to explore optical and electronic properties.In efforts to afford the enantioselective synthesis, we sought to create a library of chiral picenes in order to further study the impact of bay region substituents and terminal substituents on picene. The work towards expanding this library provided interesting information regarding the reactivity of chiral picene and some of the potential byproducts were identified.
Alkyne benzannulation is often used to generate symmetric NGs with an increase in lateral or helical elongation. While the chemical and physical properties of common NGs is relatively well established and the effects of substituents provides insight into small impacts on HOMO and LUMO energy, there is much to learn in terms of impact on the strategic removal of benzenes rings from nanographenes. Herein, we report a scope of new NGs and NG precursors to further study this influence.
Inspired by the impacts of bay region substituents, efforts towards the synthesis of a series of water-soluble NGs was analyzed from a bottom-up approach. Water-soluble NGs show promise in the use for photodynamic therapy; however, incorporation of water-solubilizing substituents was found to be best incorporated during later stages of synthesis.