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The key factors determining the emission bandwidth of thermally activateddelayed fluorescence (TADF) are investi-gated by combining computational andexperimental approaches. To achieve high internal quantum efficiencies (IQEs)in metal-free organic light emitting diode via TADF, the first triplet (T1) tofirst singlet (S1) reverse intersystem crossing (rISC) is promoted byconfiguring molecules in an electron donor-acceptor (D-A) alternation with alarge di-hedral angle, which results in a small energy gap ({\Delta}EST)between S1 and T1 levels. This allows for effective non-radiative up-conversionof triplet excitons to singlet excitons that fluoresce. However, thistraditional molecular de-sign of TADF results in broad emission spectral bands(full-width at half-maximum = 70-100 nm). Despite reports suggesting thatsuppressing the D-A dihedral rotation narrows the emission band, the origin ofemission broadening remains elusive. Indeed, our results suggest that theintrinsic TADF emission bandwidth is primarily determined by the chargetransfer character of the molecule, rather than its propensity for rotationalmotion, which offers a renewed perspective on the rational molecular design oforganic emitters exhibiting sharp emission spectra.

Charge Transfer as the Key Parameter Affecting Color Purity of TADF Emitters