Photochemistry without light - reaction of active oxalate esters with anthracenophanes

Oxalate/hydrogen peroxide chemiluminescence reaction. A 19F NMR probe of the reaction mechanism

“…The similarity of the kinetic profile from the NMR transient and the time/ intensity signal for the chemiluminescence reaction strongly suggest a common peroxyoxalate intermediate, which we proposed to be B. The results further suggest that intermediate B serves as an electron acceptor and is capable of participating in a chemically initiated electron exchange luminescence (CIEEL) mechanism (McCapra et al, 1981;Schuster and Schmidt, 1982;Givens and Schowen, 1989;Givens et al, 1989).…”

“…For almost two decades the mechanism of this chemiluminescence reaction has been of interest to chemists because of its complex nature and recently because of its application to chemical analysis at trace levels. The mechanism involves highly reactive intermediates which are alleged to activate the fluorophore through electron transfer processes (McCapra et al, 1981;Schuster and Schmidt, 1982;Givens and Schowen, 1989;Givens et al, 1989). Insight into the nature of these reactive intermediates will be of great utility in designing new oxalates and oxalate-like compounds, and in selecting optimum parameters for the chemiluminescence-based detection for trace assays (Givens el a!., 1989).…”

“…Insight into the nature of these reactive intermediates will be of great utility in designing new oxalates and oxalate-like compounds, and in selecting optimum parameters for the chemiluminescence-based detection for trace assays (Givens el a!., 1989). Rauhut (1969) and McCapra (1968) proposed dioxetanedione as the reactive intermediate which acted as the electron acceptor. The intermediacy of dioxetanedione has never received direct confirmation.…”

The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

“…In addition, the EPR detection of a biradical as a trace of the formed DOD during the reaction of the oxalyl chloride and hydrogen peroxide spectra was very recently reported [30]. CIEEL (chemically initiated electron exchange luminescence) mechanism [31,32] was applied to the PO-CL [33,34], and explained experimental evidences [35][36][37][38][39][40]. According to this mechanism, an electron transfer from the fluorophores to the HEI, such as the DOTs or DOD, takes place to form a pair consisting of the carbon dioxide radical anion and the fluorophore radical cation during the decomposition of the HEI, which is followed by a back electron transfer to produce the excited fluorophores (Scheme 1).…”

Effects of glutathione, l-cysteine, and l-methionine on the kinetics and mechanism of the peroxyoxalate–rubrene–H2O2 chemiluminescence system

“…The PO-CL reaction is thought to follow the CIEEL mechanism proposed by Schuster [12], later modified by researchers to fit the PO-CL reaction [13][14][15][16][17][18][19]. The mechanism of PO-CL process has been postulated to involve at least one highly energetic intermediate (possibly a dioxetane species) capable of exciting a fluorescent receptor molecule.…”