Abstract
Abstract. –In acidified acetonitrile, ergostatetraenone (E) efficiently quenches the tetramethyl‐1,2‐dioxetane (TMD) chemiluminescence at 410 nm, with the appearance of a new chemiluminescence at ca. 530 nm due to ergostatetraenone fluorescence. Control experiments exclude energization by triplet acetone and the trivial process (emission and reabsorption), establishing singlet‐singlet energy transfer between excited singlet acetone (A) and ground state ergostatetraenone as major pathway. From the kinetics the rate constant for singlet‐singlet energy transfer (KssA,1,) was estimated to be ca. 101 2S‐1. The chemiluminescence yield (φCL) for the TMD/ergostatetraenone system was determined to be ca. 12 × 10‐8. The fluorescence efficiency of ergostatetraenone (φ) in acidified acetonitrile is a function of acid concentration, ranging between 0.06‐0.82. The efficiency of singlet acetone production (α) was found to be 500‐fold lower than in neutral medium due to a competing acid‐catalysed, dark decomposition of TMD. A 60‐fold light enhancement has been established for this binary chemiluminescent system.
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