Solution electrogenerated chemiluminescence (ECL) was evaluated for molecules of interest for organic light-emitting diodes (OLEDs), using high-frequency voltage pulses at a microelectrode. Radical cations of different energies were electrogenerated from a series of triarylamine hole-transport materials (x-TPD), in the presence of radical anions of a high electron affinity sulfonamide derivative of tris(8-hydroxyquinoline)aluminum (Al(qs) 3 ), or a bis(isoamyl) derivative of quinacridone (DIQA). The resultant emission was from the excited singlet states 1 Al(qs) 3 * or 1 DIQA*, the same excited state produced in OLEDs based on these molecules. In solution, the majority of the reaction pairs had insufficient energy to populate 1 Al(qs) 3 * or 1 DIQA* directly, but could form the triplet states 3 Al(qs) 3 * or 3 DIQA*. The reaction order and the temporal response of the emission were consistent with subsequent formation of the excited singlet states via triplet-triplet annihilation (TTA). For reactions with a low excess Gibbs free energy to form the triplet state (∆ T G), the efficiency increased exponentially with an increase in driving force (increase in oxidation potential of x-TPD), then reached a plateau. At the maximum, the efficiencies for formation of 1 Al(qs) 3 * or 1 DIQA* via the TTA route reach as high as a few percent. The computed energetics of these reactions suggest that similar lightproducing electroluminescent reactions, proceeding via triplet formation, could also occur in condensed phase organic thin films.

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