Understanding excited-state dynamics is critical for improving the photoluminescence (PL) efficiency of exciplexes. A series of exciplexes based on conventional hole-transporting materials as donor and newly developed phenylpyridinato boron derivatives as acceptor were investigated. High PL efficiencies were achieved in only some combinations, and a large difference in performance among combinations provided insight into nonradiative processes in exciplex systems. Furthermore, the triplet local excited states (3LE) of each donor and acceptor were found play an important role in triplet exciplex harvesting. Significant contributions from triplets were clearly observed when the charge-transfer excited states (1CT and 3CT) and 3LE were ideally aligned. We also demonstrated fine control of relative energy alignment via the concentration to improve the PL efficiency.
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