Doctor of Philosophy (PHD)
Chemistry (Arts and Sciences)
Date of Defense
First Committee Member
Second Committee Member
Third Committee Member
James N. Wilson
Fourth Committee Member
The research work presented in this thesis describes the photochemical reactions carried out in the solid-state and X-ray structural studies to understand the photochemical behavior of cis-cinnamic acids by exploiting topochemical postulates. The photochemistry of excited cis-cinnamic acids can be understood from the photochemistry of corresponding trans-cinnamic acids but not from cis-cinnamic acids alone. Existence of dual reactive centers and its photoreactivity of cis-olefinic crystals are thoroughly investigated. Similar to trans-cinnamic acids, cis-cinnamic acids can also undergo direct photodimerization when the intermolecular distance of double bonds is less than 4.2 Å. Key contributing factors for the isomerization of cis-cinnamic acids are well explained. Unlike trans-cinnamic acids, polymorphic changes of cis-cinnamic acids during photoirradiation are highlighted using photochemistry and X-ray crystal structures. The role of intermolecular distance and displaced nature of reactive olefinic pairs in the photochemistry of cis-cinnamides is extensively studied. The important factors responsible for one-way isomerization of cis-cinnamides and implications of displaced nature of halogen substituted cis-cinnamides that led to multiple products are well investigated. Furthermore, uniqueness of water as a solvent is explained with the concept of “in water and on water” photoreactions of cis-cinnamic acids in an aqueous medium.
cis-Cinnamic acids; cis-Cinnamides; Topochemical postulates; Solid-state photochemistry; Geometric isomerization; "in and on water" photoreactions
Veerakanellore, Giri Babu, "Photodimerization of cis-Cinnamic Acids and cis-Cinnamides in Crystalline State and Aqueous Solution" (2018). Open Access Dissertations. 2117.
Available for download on Thursday, June 25, 2020