Positional isomeric effect: A simple and feasible strategy for constructing efficient red TADF materials

In order to investigate the effect of positional isomerization on the photoelectric properties of thermally activated delayed fluorescence (TADF) emitters, thereby fully stimulating the potential of the molecular backbone, herein, two red TADF isomers, oTPA-PPP and mTPA-PPP, were developed and synthesized by linking triphenylamine (TPA) donor into different positions of the pyrido [2′,3′:5,6] pyrazino [2,3-f] [1,10] phenanthroline (PPP). Their photoluminescent quantum yields (PLQYs) and external quantum efficiencies (EQEs) were significantly different by manipulating the substitution position of the donor. Compared with mTPA-PPP, oTPA-PPP exhibited higher PLQY benefiting from intramolecular hydrogen bonding and larger fluorescence radiative decay rate, as confirmed by both theoretical and experimental analyses. As a result, oTPA-PPP-based organic light-emitting diode (OLED) realized high EQE_max of 19.2 % with red emission at 603 nm, whereas mTPA-PPP achieves an EQE_max of 7.9 % at 596 nm. This work provides a simple and feasible molecular design strategy to design and select red TADF emitters with excellent properties.