title: Chemiluminescence in autoxidation of phosphonate carbanions. Phospha-1,2-dioxetanes as the most likely high-energy intermediates.
abstract: Autoxidation of the phosphonate carbanions derived from 9-phosphono-10-hydroacridanes provided chemiluminescence ascribed to the excited acridone anion. The intramolecular CIEEL (chemically initiated electron exchange luminescence) mechanism can be applied to this chemiluminescence because of the much higher emission efficiency compared to that of 9-phosphono-10-methylacridanes. The effect of the phosphonate substituents on the emission efficiency and especially on the rates of the chemiluminescence decay can be interpreted to originate from the valence deviation of the phosphorus atoms, which is connected with the substituent effect on the geometrical selectivity in the olefination reaction of the phosphonate carbanions. The enhanced chemiluminescence in the presence of the fluorophores was also detected in autoxidation of the carbanions of diethyl diphenylmethylphosphonate and fluorenylphosphonate. Although the evidence is circumstantial, these results strongly support the belief that phospha-1,2-dioxetane is the most likely high-energy intermediate generating the excited molecules.
authors.affiliation: Department of Chemistry, Faculty of Textile Science & Technology, Shinshu University, Ueda, Nagano 386-8567, Japan. jmotoyo@giptc.shinshu-u.ac.jp
authors.forename: Jiro
authors.initials: J
authors.lastname: Motoyoshiya
authors.forename: Tsuneaki
authors.initials: T
authors.lastname: Ikeda
authors.forename: Shuji
authors.initials: S
authors.lastname: Tsuboi
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Kusaura
authors.forename: Yoshino
authors.initials: Y
authors.lastname: Takeuchi
authors.forename: Satoko
authors.initials: S
authors.lastname: Hayashi
authors.forename: Sachiko
authors.initials: S
authors.lastname: Yoshioka
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Takaguchi
authors.forename: Hiromu
authors.initials: H
authors.lastname: Aoyama