Abstract

AbstractAdvanced organoboron dyes, incorporating tetra‐boron difluoride (tetra‐BF2) moieties, are developed, demonstrating efficient electrochemiluminescence (ECL) emissions in the green to orange regions through direct ion annihilation. By introducing diverse alkyl modifications in the molecules, luminescence color tuning is achieved via alterations in conjugation and bending angle. A photoluminescence quantum yield of 100% in dilute solutions is successfully achieved. Notably, the introduction of alkyl groups to the methine side stabilizes the radical ionic state, resulting in a high ECL efficiency of 74% through an efficient radical‐ion annihilation pathway. The key factor is that the energy of the annihilation reaction exceeds the S1 energy required for luminescence. Spin density calculations further elucidate the substituent effects on the radical ions of complexes. Moreover, the lasing properties of these materials in the solution‐processed blend films are investigated, revealing a low amplified spontaneous emission (ASE) threshold (Eth) of 6.40 ± 0.24 µJ cm−2, which is notably lower among organic laser materials. This is attributed to their large Stokes shifts and high quantum yield. The excellent ECL and ASE performances establish these materials as a valuable addition to the existing library of organoboron dyes, offering fresh insights into the development of organic solid‐state lasers.

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