NATURE OF LOWEST TRIPLET CONFIGURATION OF FLAVINS

Abstract— The phosphorescence spectrum of riboflavin has been reexamined at 77°K in an ethylene glycol: water matrix. The phosphorescence occurs at approximately the 605 nm (ca. 2‐·05 eV) region, in reasonable agreement with the theoretical calculations of 1·6–1·8 eV [21]. The emission was found to be negatively polarized, and to have a relatively long lifetime (0·56 sec). On the basis of this data and additional theoretical results, it is concluded that the lowest triplet of riboflavin is of 3(τ,τ*) type. Upon addition of potassium iodide, the phosphorescence emission is enhanced through spin‐orbit perturbation. The presence of oxygen (atmospheric pressure) in the frozen glass apparently has no effect on the emission. The phosphorescence spectra of alloxazine are also presented. Results of the present work have been applied to the photodephosphorylation of menadiol diphosphate in elucidating its mechan ism involving the riboflavin triplet and singlet oxygen. Copyright © 1969, Wiley Blackwell. All rights reserved