Zhai Lu, Yuan Jiayi, Huang Jianyi, Pan Xue-Wei, Wan Li, Ning Weihua, Ren Xiao-Ming
State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry and Molecular Engineering, Nanjing Tech University, Puzhu South Road 30, Nanjing, 211816, P.R. China.
Institute of Functional Nano & Soft Materials (FUNSOM), Joint International Research Laboratory of Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, 215123, P.R. China.
Angew Chem Int Ed Engl. 2025 Jun 2;64(23):e202425543. doi: 10.1002/anie.202425543. Epub 2025 Mar 25.
Circularly polarized luminescence (CPL)-active materials have attracted considerable attention due to their potential applications in various advanced technological fields. CPL activity typically requires compounds that crystallize in noncentrosymmetric chiral space groups. Achieving noncentrosymmetric crystal structures using achiral molecular architectures is highly appealing but remains a significant challenge. Herein, we present a strategy for designing and synthesizing high-performance CPL materials via crystallization-driven self-assembly using achiral architectures. We successfully obtained Mn-based halide enantiomeric hybrids (P-1 and M-1), self-assembled from [MnBr] anions and rotational symmetric [Pr-dabco] cations (Pr-dabco = 1-propyl-1,4-diazabicyclo-[2.2.2]octan-1-ium), crystallizing in the chiral space group P222. The single crystals of 1 exhibit exceptionally high CPL performance, with a luminescence dissymmetry factor |g| and photoluminescence quantum yield (PLQY) up to 4.8 × 10 and 86.8%, respectively, thus a record-high figure of merit (FM) of 4.2 × 10 among reported Mn-based CPL materials. Furthermore, P/M-1 based UV-LED devices demonstrated outstanding light-emitting performance, including high color-purity, excellent stability, remarkable luminous brightness (74 591.94 cd m), and a high electroluminescence dissymmetry factor (g) value of 3.2 × 10. This study offers a robust strategy for the design and development of high-performance CPL materials utilizing achiral molecular architectures.
圆偏振发光（CPL）活性材料因其在各种先进技术领域的潜在应用而备受关注。CPL活性通常要求化合物在非中心对称手性空间群中结晶。使用非手性分子结构实现非中心对称晶体结构极具吸引力，但仍然是一项重大挑战。在此，我们提出了一种通过使用非手性结构的结晶驱动自组装来设计和合成高性能CPL材料的策略。我们成功获得了基于锰的卤化物对映体杂化物（P-1和M-1），它们由[MnBr]阴离子和旋转对称的[Pr-dabco]阳离子（Pr-dabco = 1-丙基-1,4-二氮杂双环-[2.2.2]辛烷-1-鎓）自组装而成，在手性空间群P222中结晶。1的单晶表现出极高的CPL性能，发光不对称因子|g|和光致发光量子产率（PLQY）分别高达4.8×10和86.8%，因此在报道的基于锰的CPL材料中具有创纪录的高优值（FM）4.2×10。此外，基于P/M-1的紫外发光二极管器件表现出出色的发光性能，包括高色纯度、优异的稳定性、显著的发光亮度（74591.94 cd m）以及高达3.2×10的高电致发光不对称因子（g）值。这项研究为利用非手性分子结构设计和开发高性能CPL材料提供了一种有力的策略。
