Despite the emergence of interlayers with high triplet energies (T₁) to stabilize blue phosphorescent organic light-emitting diodes (PhOLEDs), a limited understanding of their molecular structures poses a challenge in preventing triplet exciton leakage while maintaining charge balance. Here, we report a rational design strategy for interlayers aimed at concurrently controlling T₁ and molecular arrangements conducive to charge transport. Four interlayer materials having high T₁ (∼3.0 eV) are developed as electron-blocking materials (EBMs), utilizing asymmetric orthogonal geometries with varying torsion angles and dipole moments. X-ray crystallographic analyses reveal that the EBM, featuring the most asymmetric charge distributions, exhibits a herringbone packing and a face-on orientation through dipole-induced anisotropic interactions, thereby promoting hole transport. The power efficiency and operational lifetime of the corresponding blue PhOLEDs increase by 24% and 21%, respectively, compared with a conventional EBM. This study offers extensive insights into designing interlayers with versatile applicability in optoelectronics harnessing triplets.

尽管出现了具有高三重态能量（T ₁ ）的中间层来稳定蓝色磷光有机发光二极管（PhOLED），但对其分子结构的有限了解对防止三重态激子泄漏同时保持电荷平衡提出了挑战。在这里，我们报告了一种合理的中间层设计策略，旨在同时控制有利于电荷传输的 T ₁和分子排列。四种具有高T ₁ (∼3.0 eV) 的中间层材料被开发为电子阻挡材料(EBM)，利用具有不同扭转角和偶极矩的不对称正交几何形状。 X射线晶体学分析表明，EBM具有最不对称的电荷分布，通过偶极子诱导的各向异性相互作用表现出人字形堆积和面对面取向，从而促进空穴传输。与传统的 EBM 相比，相应的蓝色 PhOLED 的功率效率和工作寿命分别提高了 24% 和 21%。这项研究为设计中间层提供了广泛的见解，在光电三元组中具有多种适用性。