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Influence of confined media on photophysical and photochemical transformations of organic guest molecules: Water soluble supramolecules as confined media

Posted on:2009-02-22Degree:Ph.DType:Thesis
University:University of MiamiCandidate:Venkata, Srirama N. MaddipatlaFull Text:PDF
GTID:2441390002996741Subject:Chemistry
Abstract/Summary:
For more than 150 years, since the synthesis of urea by Friedrich Wohler in 1828, molecular chemistry has developed a vast array of highly sophisticated and powerful methods for the construction of more complex molecular structures. Beyond the molecular chemistry based on the covalent bond, there lies the field of supramolecular chemistry, aims to gain control over the intermolecular bond. Supramolecular species are characterized both by the spatial arrangement of their components and by the nature of the intermolecular bonds that hold these components together.*;1D and 2D NMR experiments were used to understand the orientation of guest molecules within the host systems. Room temperature phosphorescence from thioketones, conformational dependent product distribution from benzoin ethers and controlling the bimolecular photodimerization reactions in host cavities have been investigated during the course of this research. Furthermore, the photodimerization experiments were investigated in dynamic media and proposed an intuitive model to predict the outcome beforehand.;*Please refer to dissertation for diagrams. 1Lakshmi S. Kaanumalle, R. Ramesh, Murthy V. S. N. Maddipatla, Jayaraj Nithyanandhan, Narayanaswamy Jayaraman, V. Ramamurthy. "Dendrimers as Photochemical Reaction Media. Photochemical Behavior of Unimolecular and Bimolecular Reactions in Water-Soluble Dendrimers." J. Org. Chem. 2005, 70, 5062--5069. 2 Murthy V. S. N. Maddipatla, Lakshmi S. Kaanumalle, Arunkumar Natarajan, Mahesh Pattabiraman, and V. Ramamurthy. "Preorientation of Olefins toward a Single Photodimer: Cucurbituril-Mediated Photodimerization of Protonated Azastilbenes in Water." Langmuir 2007, 23, 7545--7554.;The photophysical and photochemical behavior of the encapsulated guest molecules within supramolecular assemblies has been investigated. We have chosen rigid host systems (Cucurbiturils and Octa acid)1 and dynamic host systems (Dendrimers and Micelles)2 and exploited their interiors for conducting specific photochemical reactions.
Keywords/Search Tags:Photochemical, Guest molecules, Host systems, Media
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