Wang Tianhao, Zhang Zeyuan, Hao Aiyou, Xing Pengyao
School of Chemistry and Chemical Engineering, Shandong University Jinan 250100 PR China
Chem Sci. 2025 Jan 10;16(8):3498-3508. doi: 10.1039/d4sc07859d. eCollection 2025 Feb 19.
Noncovalent forces have a significant impact on photophysical properties, and the flexible employment of weak forces facilitates the design of novel luminescent materials with a variety of applications. The arene-perfluoroarene (AP) force, as one type of π-hole/π interaction, shows unique directionality, involving an electron-deficient π-hole interacting with a π-electron-rich region, facilitating precise orientation and stabilization in supramolecular structures. Here we present an amination engineering protocol to build a perfluoroarene library based on an octafluoronaphthalene skeleton with various steric and electronic properties. In diluted solution-based assemblies, the perfluoroarenes perform as efficient molecular barriers to perylene building units, lighting up the luminescence. Enhanced steric effects, hydrophobicity and appended aromatic pendants are pivotal structural factors to boost the molecular barrier effect. Highly affinitive AP coassemblies transfer chirality from perfluoroarenes to achiral perylene moieties, inducing the appearance of chiral microstructures with tailored circularly polarized luminescence. Application as luminescent ink for enhanced water-resistance in displays and anti-counterfeiting is successfully realized. This work greatly extends the potential of molecular engineering in noncovalently bonded luminescent materials, and clearly reveals structure-property correlations.
非共价力对光物理性质有重大影响，灵活运用弱力有助于设计具有多种应用的新型发光材料。芳烃 - 全氟芳烃（AP）力作为一种π - 空穴/π相互作用，表现出独特的方向性，涉及缺电子的π - 空穴与富π电子区域相互作用，有助于超分子结构中的精确取向和稳定。在此，我们提出一种胺化工程方案，以构建基于具有各种空间和电子性质的八氟萘骨架的全氟芳烃库。在基于稀释溶液的组装体中，全氟芳烃对苝构建单元起到有效的分子屏障作用，点亮发光。增强的空间效应、疏水性和附加的芳环侧链是增强分子屏障效应的关键结构因素。高度亲和的AP共组装体将手性从全氟芳烃转移到非手性的苝部分，诱导出具有定制圆偏振发光的手性微结构。成功实现了作为增强显示器防水性和防伪的发光墨水的应用。这项工作极大地扩展了非共价键合发光材料中分子工程的潜力，并清楚地揭示了结构 - 性质的相关性。
