Steric Modulation of Spiro Structure for Highly Efficient Multiple Resonance Emitters

A multiple resonance thermally activated delayed fluorescence (MR‐TADF) molecule with a fused, planar architecture tends to aggregate at high doping ratios, resulting in broad full width at half maximum (FWHM), redshifting electroluminescence peaks, and low device efficiency. Herein, we propose a mono‐substituted design strategy by introducing spiro‐9,9′‐bifluorene (SBF) units with different substituted sites into the MR‐TADF system for the first time. As a classic steric group, SBF can hinder interchromophore interactions, leading to high device efficiency (32.2–35.9 %) and narrow‐band emission (≈27 nm). Particularly, the shield‐like molecule, SF1BN, seldom exhibits a broadened FWHM as the doping ratio rises, which differs from the C3‐substituted isomer and unhindered parent emitter. These results manifest an effective method for constructing highly efficient MR‐TADF emitters through a spiro strategy and elucidate the feasibility for steric modulation of the spiro structure in π‐framework. By incorporating a three‐dimensional spiro unit into multiple resonance thermally activated delayed fluorescence emitters, the device efficiency is increased to nearly 1.5 times that of the unhindered emitter. Notably, the linkage pattern with spatial interaction and hindrance can maintain the narrow FWHM and curb unfavorable redshifts at a high doping ratio.