Abstract
Abstract— The ternary chemiluminescent system consisting of tetramethyl‐dioxetane (TMD), 9,10‐dibromoanthracene (DBA) and rubrene (Ru) has been investigated in benzene solution and in polystyrene matrices. DBA has been found to mediate the energy transfer between excited triplet acetone (3K), generated from TMD, and rubrene resulting in the enhancement of the Ru emission and reduction in the DBA emission. A detailed kinetic analysis confirms that ca. 50% of the enhanced chemilumines‐cence involves triplet‐singlet (TS) energy transfer from 3K to DBA, followed by singlet‐singlet (SS) energy transfer from DBA to Ru, the remainder ca. 50% being due to reabsorption of DBA fluorescence by rubrene. It is concluded that the TS energy transfer is of the resonance type, occurring with a rate of kTSK.DBA= (1.4 ± 0.4) ± 109M‐1s‐1 and an efficiency of øTSK.DBA= 0.3 ± 0.1. As expected, the SS energy transfer is also of the resonance type, taking place at comparable rates in benzene solution and in polystyrene matrices, is. kSSDBARU= 1.5 ± 1010 M‐1 and (2.2 ± 0.2) ± 1010M‐1s‐1, respectively.
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