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Title:The Chemistry of Aroyl Azides in Piperidine- and Steroid-Separated Bichromophoric System: Photoinduced Long-Distance Intramolecular Electron Transfer Reactions
Author(s):Zhu, Yong
Doctoral Committee Chair(s):Schuster, Gary B.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Chemistry, Organic
Chemistry, Physical
Abstract:The photochemistry and photophysics of piperidine- and steroid- separated bichromophoric systems containing an aroyl azide as the electron acceptor and secondary aromatic amines as the electron donors was examined. We report the first example of unique photochemical reactivity associated with through-bond electron transfer in these bichromophores. Light absorbed by the aroyl azide acceptor chromophore of these compounds gives isocyanate by the photo-Curtius rearrangement and nitrene by loss of nitrogen. Light absorbed by the aryl amine donor chromophores initiates a through-bond electron-transfer reaction to form high energy, charge-separated intermediate states. The aryl amine radical cations were detected by pulsed laser spectroscopy and the highly reactive aroyl azide radical anions were identified by the results of steady-state photolysis. In acetonitrile and in methyl alcohol solution, the photoexcited aryl amine converts the azide to a primary amide. The mechanism of this reaction is thought to involve long-range electron transfer to form first the azide and then nitrene radical anion intermediates. Similar irradiation of the bichromophoric system in cyclohexane solution converts the azide to a secondary amide. In this case the reaction seems to proceed through a nitrene intermediate. The photolysis efficiency of the azide is solvent-independent, and is not affected significantly by the orientation of amine group (the cis or trans). Intramolecular electron-transfer from the singlet and triplet excited state of the donor chromophore plays an important role and triplet-triplet energy transfer mechanism may also be involved in this chemistry. The mechanism for the reaction is supported by fluorescence quenching and laser flash photolysis experiments and by quenching and trapping studies.
Issue Date:1992
Type:Text
Description:163 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1992.
URI:http://hdl.handle.net/2142/72275
Other Identifier(s):(UMI)AAI9305750
Date Available in IDEALS:2014-12-17
Date Deposited:1992


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