Precisely Regulation of Peripheral Decoration of Multi‐Resonance Molecules and Construction of Highly Efficient Solution‐Processed Orange–Red OLEDs with External Quantum Efficiency Approaching 20%

Abstract The advent of multi‐resonance thermally activated delayed fluorescence (MR‐TADF) materials, heralding cutting‐edge emitters with superior efficiency and color fidelity, represents a momentous stride in the realm of organic light‐emitting diodes (OLEDs). In this particular investigation, substantial advancements have been made by enhancing, synthesizing, and characterizing three distinct MR‐type emitters through meticulous control of peripheral decorations using frontier molecular orbital engineering. Through strategic attachment of various pyrimidine derivatives to the positions of the lowest unoccupied molecular orbitals (LUMO) of the parent molecule, the molecular excited state attributes are meticulously tailored, leading to the development of orange‐red MR‐TADF emitters. These designed molecules have demonstrated an emission spectrum shift from orange‐red to orange, exhibiting peak wavelengths spanning the range of 585–608 nm and full width at half‐maximums (FWHM) between 36 and 43 nm. This signifies a remarkable precision in managing the emission maxima of MR‐TADF emitters. Astonishingly, the solution‐processed OLEDs have showcased vibrant orange‐red electroluminescence, characterized by peak wavelengths ranging from 587 to 611 nm, accompanied by a notable external quantum efficiency nearing 20%.