香港中文大学赵征团队揭示了高效室温磷光的孤对介导多重穿越空间相互作用。相关论文于2025年3月18日发表于国际顶尖学术期刊《美国化学会杂志》上。

三重态激子的同时产生和稳定是实现高效有机室温磷光（RTP）的关键，但由于其机理和结构-性质关系尚不明确，因此具有挑战性。

本文提出了一种单对介导的多重穿越空间相互作用（TSIs）策略来有效地诱导RTP。通过结合杂原子来促进空间n-n和nπ相互作用时，孤对在整个结构中离域，导致激发态能级的密集分裂。它们出现了更匹配的能级，单重态和三重态之间的能量间隙较小（ΔEST），导致多个系统间交叉（ISC）过渡通道，有助于三重态激子的产生。强TSIs还能有效地固化分子结构，稳定辐射的三重态激子。

此外，控制TSIs强度可以提高RTP的效率，延长持续时间，并对高温具有耐受性。这项工作不仅从一个新的角度探索了RTP机制的基本原理，而且为ISC的促进和三激子的稳定提供了一种通用的策略。

附：英文原文

Title: Lone Pairs-Mediated Multiple Through-Space Interactions for Efficient Room-Temperature Phosphorescence

Author: Fulong Ma, Bo Wu, Siwei Zhang, Jinhui Jiang, Jinghong Shi, Zeyang Ding, Yue Zhang, Haozhe Tan, Parvej Alam, Jacky W. Y. Lam, Yu Xiong, Zhen Li, Ben Zhong Tang, Zheng Zhao

Issue&Volume: March 18, 2025

Abstract: The simultaneous generation and stabilization of triplet excitons are the key to realizing efficient organic room temperature phosphorescence (RTP), which is challenging owing to the obscure mechanism and structure–property relationships. Herein, a strategy of lone-pair-mediated multiple through-space interactions (TSIs) is proposed to availably induce RTP. By incorporating heteroatoms to facilitate through-space n–n and nπ interactions, the lone pairs are delocalized throughout the structure, resulting in the dense splitting of the excited-state energy levels. Thus, more matched energy levels with a small energy gap between singlet and triplet states (ΔEST) emerge, resulting in multiple intersystem crossing (ISC) transition channels that assist triplet excitons generation. The strong TSIs also effectively rigidify the molecular structures and thus stabilize triplet excitons for radiation. Furthermore, the manipulation of TSI intensity allows efficiency enhancement, persistent time prolongation, and tolerance to high temperatures of RTP. This work not only explores the fundamental principle of the RTP mechanism from a new view but also provides a universal strategy for ISC promotion and triple excitons stabilization.

DOI: 10.1021/jacs.5c02567

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c02567