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The naphthalene sensitized photoracemization of sulfoxides


Cooke, Robert Sanderson (1970) The naphthalene sensitized photoracemization of sulfoxides. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/AYK6-7Q95.


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.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Hammond, George Simms
Thesis Committee:
  • Unknown, Unknown
Defense Date:10 September 1969
Record Number:CaltechTHESIS:04192011-132638953
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:6339
Deposited By: Tony Diaz
Deposited On:27 Apr 2011 16:45
Last Modified:21 Dec 2019 01:30

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