Synthesis and Electrochemiluminescence of a Di-Boron Thermally Activated Delayed Fluorescence Emitter

Recent advances in electrochemiluminescence (ECL) leveraging thermally activated delayed fluorescence (TADF) have highlighted its potential for near-unity exciton harvesting. However, there are still very limited examples of TADF-ECL emitters. We present a rigid diboron-embedded multiple-resonance TADF emitter, which exhibits blue-green emission at 493 nm with a remarkably narrow bandwidth (FWHM = 22 nm) and minimized singlet-triplet energy gap (ΔE_ST = 0.2 eV), achieving a 67% photoluminescence quantum yield. DFT calculations confirm the short-range charge transfer, enabling narrowband emission. Co-reactant-dependent ECL shows that tripropylamine (TPrA) improves the ECL efficiency from 11% (annihilation) to 51%, while benzoyl peroxide (BPO) yields 1% due to poor radical stabilization. ECL spectra align with photoluminescence, confirming the singlet-state dominance without exciplex interference. TPrA enhances stable radical formation and energy transfer, whereas BPO induces non-radiative losses. These findings establish molecular rigidity and co-reactant selection as pivotal factors in developing high-performance TADF-ECL systems, providing fundamental guidelines for designing organic electrochemiluminescent materials with optimized exciton harvesting efficiency.