Chemiexcitation Efficiency of Intermolecular Electron-transfer Catalyzed Peroxide Decomposition Shows Low Sensitivity to Solvent-cavity Effects

Intermolecular chemically initiated electron exchange luminescence (CIEEL) systems are known to possess low chemiluminescence efficiency; whereas, the corresponding intramolecular transformations are highly efficient. As the reasons for this discrepancy are not known, we report in this work our studies of the solvent‐cavity effect on the efficiency of two intermolecular CIEEL systems, the catalyzed decomposition of diphenoyl peroxide and of a relatively stable 1,2‐dioxetanone derivative, spiro‐adamantyl‐1,2‐dioxetanone. The results indicate a very low medium viscosity effect on the quantum yields of these systems, a priori not compatible with these bimolecular transformations, showing also that their low efficiency cannot be due to solvent‐cavity escape of intermediate radical ion pairs. In addition, the solvent‐cage effect on the CIEEL efficiency, after the occurrence of the initial electron transfer, proved also to be very low, indicating the intrinsic low viscosity effect on the chemiexcitation step. Therefore, it is concluded that the low efficiency of these systems is intrinsic to the chemiexcitation step and cannot be improved by medium viscosity effects, being possibly due to sterical hindrance on charge‐transfer complex formation in the initial step of the CIEEL. The low quantum yields determined in the rubrene and perylene catalyzed decomposition of diphenoyl peroxide and spiro‐adamantyl‐1,2‐dioxetanone are not subject to significant solvent cavity effects in binary ethyl acetate/dibutyl phthalate mixtures, indicating that the low efficiency is not due to solvent cavity escape of intermediate radical pairs but might be caused by steric effects on the interaction between the peroxide and the catalyst.