Chemiluminescence of Diphenoyl Peroxide. Chemically Initiated Electron Exchange Luminescence. A New General Mechanism for Chemical Production of Electronically Excited States.

摘要

The thermal reactions of diphenoyl peroxide (1) were probed. It was found that when 1 was heated at 24 for 24 h in CH2C12 benzocoumarin (2) and a small amount of polymeric peroxide were formed. Under these conditions the reaction was essentially non-chemiluminescent. However, addition of any one of several easily oxidized fluorescent molecules resulted in readily detected chemiluminescence. The mechanism for chemical light formation was probed by investigating the: (I) effect of additives' structure, (II) reaction kinetics, (III) effect of solvent polarity and viscosity, (IV) effect of reaction conditions on the products, v) chemiluminescence emission, and (VI) independent generation of proposed intermediates. These studies show that the chemiluminescence of 1 does not proceed by the one of the classical mechanisms. We propose a new general chemical light producing scheme identified as chemically initiated electron exchange luminescence. (Author)