Synthesis and application of novel trisresorcinarenes and investigation of new photochemical processes of chromophores
Date of Award
Doctor of Philosophy in Chemistry
Two fields of organic chemistry with a prominent presence in many research groups are supramolecular chemistry and photochemistry. These fields continue to grow and spread their influence in many industries and research areas. The first two chapters of this dissertation focus on the studies and applications of the macrocyclic isomers Noria and trisresorcinarene (R3). The development of their respective rotaxanes via the slipping method was examined and how the incorporation of the linear thread molecule affects the binding properties of the exterior pockets for target gas molecules: CO2, Xe, and Kr. Additionally, a novel water-soluble version of Noria and R3 were synthesized via the addition of twelve sulfonatomethyl groups. These sulfonated macrocycles were then purposed as sulfonic acid catalysts for the Pechmann and Biginelli condensations. These heterogeneous, phase-transfer catalysts showed excellent yield over a broad scope of substrates for the reactions. The high applicability and recyclability in addition to the ease and scalability of their preparation makes the sulfonated Noria and R3 potential catalysts for industrial scale reactions.
The second two chapters focus on the photochemistry of two prominent chromophores in the field: coumarin and acridine. 7-hydroxycoumarin (7HC) has been used as a photoacid for the formation of a proton upon the irradiation with UV light. This study looks towards the conjugate coumarin oxide anion as a source of a strong nucleophilic chromophore without the use of heat or basic reaction conditions. This photosubstitution was studied for its mechanistic trends and its applicability for the chemical staining of biological substrates, such as peptides and carbohydrates. Finally, the final chapter look at the anaerobic photooxidation of acridine methanol derivatives. The study will focus on the difference of reactivities between hydroxymethyl groups on various carbon positions of the chromophore ring. Additionally, DFT and TD-DFT calculations were performed on the acridines to provide further insight into the electronic structure of the excited state and therefore, the mechanism of the oxidation upon absorption of a photon. These experiments can help understand the photochemistry of acridine derivatives in the excited state to further develop these chromophores for photoredox agents.
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Hasselbrink, Carson Lawrence, "Synthesis and application of novel trisresorcinarenes and investigation of new photochemical processes of chromophores" (2022). Open Access Dissertations. Paper 1450.
Available for download on Wednesday, September 06, 2023