Synthesis, Derivatization, and Application of Carbon Nanohoops and Macrocycles via Alkyne Metathesis
Degree
Doctor of Philosophy (PhD)
Department
Chemistry
Document Type
Dissertation
Abstract
Carbon nanohoops are radially oriented, carbon-rich materials with fully conjugated π-systems that face inward towards one another. Of these, cycloparaphenyleneacetylene (CPPA) and cycloparaphenylene (CPP) nanohoops have been extensively studied for their optoelectronic, supramolecular, and strain-promoted reactivity since their respective inceptions. Chapter 1 discusses the synthesis of these nanohoops and other macrocycles through various methods, mainly through alkyne metathesis of shape-persistent monomers. In addition, this chapter provides a history of the strain-promoted reactivity of CPPs, CPPAs, and macrocycles containing strained alkynes. Chapter 2 primarily discusses the synthesis and strain-promoted reactivity of a novel, fluorene-derived CPPA carbon nanohoop, Fl-[6]CPPA. This study demonstrates the development of its modular synthesis as well as its selective participation in strain-promoted azide-alkyne cycloaddition (SPAAC). Our findings are supported by computations performed by the Wu group at the University of Houston. Chapter 3 focuses on the development of pillararene-inspired macrocycles (PIMs) via alkyne metathesis to construct PIM moieties with large, rigid central cavities. A review is provided on the synthetic history of large pillararenes and PIMs. We show how these macrocycles can be synthesized in good yields in five steps using alkyne metathesis as a macrocyclization strategy. To further the idea that shape-persistent monomers with varying central arene groups can produce macrocycles through alkyne metathesis in good yields, Chapter 4 details various completed and ongoing collaborations between our group and the Tahara group at Meiji University in Tokyo, Japan, the Starý group at IOCB Prague in the Czech Republic, and the Rickhaus group at the University of Geneva in Switzerland.
Date
11-3-2025
Recommended Citation
Herman, Robert, "Synthesis, Derivatization, and Application of Carbon Nanohoops and Macrocycles via Alkyne Metathesis" (2025). LSU Doctoral Dissertations. 6950.
https://repository.lsu.edu/gradschool_dissertations/6950
Committee Chair
Lee, Semin