Insights into electrochemiluminescence dynamics by synchronizing real-time electrical, luminescence, and mass spectrometric measurements.

Electrochemiluminescence (ECL) comprises a sophisticated cascade of reactions. Despite advances in mechanistic studies by electrochemistry and spectroscopy, a lack of access to dynamic molecular information renders many plausible ECL pathways unclear or unproven. Here we describe the construction of a real-time ECL mass spectrometry (MS) platform (RT-Triplex) for synchronization of dynamic electrical, luminescent, and mass spectrometric outputs during ECL events. This platform allows immediate and continuous sampling of newly born species at the Pt wire electrode of a capillary electrochemical (EC) microreactor into MS, enabling characterization of short-lived intermediates and the multi-step EC processes. Two ECL pathways of luminol are validated by observing the key intermediates α-hydroxy hydroperoxide and diazaquinone and unraveling their correlation with applied voltage and ECL emission. Moreover, a "catalytic ECL route" of boron dipyrromethene (BODIPY) involving homogeneous oxidation of tri- n -propylamine with the BODIPY radical cation is proposed and verified.