Cooke, Robert Sanderson (1970) The naphthalene sensitized photoracemization of sulfoxides. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:04192011-132638953
The sensitized photoracemization of alkyl aryl sulfoxides has been shown to result from energy transfer from the singlet state of naphthalene. The possibility of exothermic electronic energy transfer has been ruled out on the basis of spectroscopic data. It is postulated that an exciplex is reversibly formed from an excited singlet state naphthalene molecule and a ground state molecule of the sulfoxide. This excited complex then undergoes radiationless decay converting electronic energy to vibrational energy partitioned between the two components of the exciplex. Enough vibrational energy appears in the aryl sulfinyl center to effect thermal pyramidal inversion with high efficiency. Steric and electronic effects on the rates of fluorescence quenching or of photoracemization are small.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||10 September 1969|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Tony Diaz|
|Deposited On:||27 Apr 2011 16:45|
|Last Modified:||26 Dec 2012 04:34|
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