Rationalizing the role of electron/charge transfer in the intramolecular chemiexcitation of dioxetanone-based chemi-/bioluminescent systems
The thermolysis of dioxetanones is a key process in the intramolecular chemiexcitation step of several chemi-and bioluminescent reactions. This step is generally explained with mechanisms based on either electron transfer (ET), such as the Chemically Initiated Electron-Exchange Luminescence (CIEEL) mechanism, or charge transfer (CT), such as the Charge Transfer-Initiated Luminescence (CTIL) mechanism. Here, we have used a TD-DFT approach to characterize the thermolysis and chemiexcitation ste...