PART I. INTRAMOLECULAR ENERGY TRANSFER ACROSS AN ESTER BRIDGE: A STUDY OF THE SPHERE OF QUENCHING MODEL. PART II. THE STEREOCHEMISTRY OF 4-BENZOYL-2,3-DIAZABICYCLO (2.2.2) OCT-2-ENE
WALLER, ANDREW STUART
Master of Arts
Part I. A series of bichromophoric molecules linked by an ester bridge is synthesized, and their photochemical and intramolecular energy transfer properties are examined. If benzophenone and naphthalene are held approximately 10 A apart by this ester bridge rather than by an alkyl chain, intramolecular energy transfer is only 93% to 97% complete in a frozen glass, rather than 100% complete. This value shows the previous critical radius of 13 A from the sphere of quenching model to be too long. The reason and rationalization for this loss of energy transfer efficiency is explored. Several irradiation experiments are also conducted, studying both intramolecular and intermolecular energy transfer along competing pathways. Part II. The stereochemistry of 4-benzoyl-2,3-diazabicyclo(2.2.2) oct-2-ene is studied using various two-dimensional NMR techniques.