Photo sensitive, photoacid, photo retro diels alder reaction


Light as a “green” source of energy has become increasingly attractive throughout the past century and has shown versatility for the application of activating chemical reactions. Compared with traditional energy sources, it provides a more direct, selective and controllable method. My PhD study was focused on the study of photochemistry of organic materials in two different systems. The first system is regarding reversible photoacids which generate protons on irradiation. With the aim of systematically studying these novel types of long lived photoacids, a series of photoacids was designed, synthesized and whose chemical mechanism was thoroughly investigated. This type of photoacid changes from a weak acid to a strong acid with a pH change of several units, which achieves nearly complete proton dissociation upon visible light irradiation. The whole process is reversible and the half-life of the proton-dissociation state is long enough to be used in many applications. Besides fundamental studies, different applications based on this type of photoacids were also completed. An esterification reaction was catalyzed and the volume of a pH-sensitive polymer was altered due to the large amount of photo generated protons from this photoacid. A reversible electrical conductivity change of polyaniline (PANI) was also achieved by doping with this reversible photoacid. In order to induce a large conductivity increase, an irreversible photoacid generator (PAG) was embedded in a novel PANI/PAG/PVA novel composition. In this system, Poly (vinyl alcohol) (PVA) forms a hydrogen-bonding network to facilitate proton transfer between the PAG and PANI. A final electrical conductivity of 10-1 S cm-1 was successfully achieved after irradiation. The second system in which I explored photochemistry of organic molecules concerns Photoretro-Diels-Alder (PrDA) reactions and a variety of Diels-Alder (DA) adducts were designed for these studies. UV light was used to trigger the retro-Diels-Alder reactions. Quantum yield of iv each DA adducts was investigated. This revealed that the photo-reactivity of this process depends on the electron-donating ability of the diene and the electron-withdrawing ability of the dienophile component. Mechanistic studies of this PrDA reaction reveal that a charge-separated intermediate is generated from a singlet excited state. This was applied to an unsaturated cyclic α-diketones (DKs), which underwent PrDA reactions and generated anthracene derivatives and carbon monoxide (CO), which itself plays profound and important roles in biological systems. These unsaturated cyclic α-diketones (DKs) encapsulated in micelles are effective CO-releasing molecules (CORMs) and are capable of carrying and releasing CO in cellular systems. This novel type of organic CORMs has potentially low toxicity and generates fluorescence, which provides a useful tool for the study of the biological functions of CO.


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Graduation Date





Liao, Yi


Doctor of Philosophy (Ph.D.)


College of Sciences



Degree Program









Release Date

December 2014

Length of Campus-only Access

1 year

Access Status

Doctoral Dissertation (Open Access)


Dissertations, Academic -- Sciences, Sciences -- Dissertations, Academic

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Chemistry Commons