Although the π–π stacking has been widely applied for constructing aggregated emitters in optoelectronics fields, the role of intramolecular non‐covalent π–π interactions has not been well studied. Here, a supramolecular foldermer M‐σ‐C, with the electron donor (D) and acceptor (A) units spatially separated with a non‐covalent bond at a close distance by methylene linker is designed and synthesized. This gives a face‐to‐face D/A stacking configuration with supramolecular π–π interactions. Temperature‐dependent nuclear magnetic resonance measurements and single crystal analyses confirm its folding configuration. In solutions, M‐σ‐C exhibits a single‐molecule exciplex thermally activated delayed fluorescence (TADF) property ascribing to the efficient intramolecular through‐space charge transfer (CT) process. While single‐molecule deep‐blue room temperature phosphorescence (RTP) with a long afterglow lifetime of 236 ms is observed in a nonpolar matrix, which represents the record lifetime among current 3CT‐character featured RTP. This work indicates that intramolecular non‐covalent interactions play an important role in manipulating high‐performance single‐molecule exciplex TADF and RTP, and provide a feasible molecular design strategy for supramolecular chemistry involving the development of optoelectronic materials.

中文翻译：

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通过分子折叠体中的非共价 π-π 相互作用操纵单分子激基复合物 TADF 和深蓝 RTP

虽然π-π堆叠已广泛应用于构建光电子领域的聚集发射器，分子内非共价键的作用π-π相互作用尚未得到充分研究。在这里，设计并合成了超分子文件夹M-σ-C，其电子供体（D）和受体（A）单元通过亚甲基连接体以近距离非共价键空间分离。这给出了具有超分子的面对面D/A堆叠结构π-π互动。温度依赖性核磁共振测量和单晶分析证实了其折叠构型。在溶液中，M-σ-C 表现出单分子激基复合物热激活延迟荧光（TADF）特性，归因于有效的分子内空间电荷转移（CT）过程。而在非极性基体中观察到的单分子深蓝色室温磷光（RTP）具有236 ms的长余辉寿命，这代表了当前寿命的记录3CT 字符以 RTP 为特色。这项工作表明分子内非共价相互作用在操纵高性能单分子激基复合物TADF和RTP中发挥着重要作用，并为涉及光电材料开发的超分子化学提供了可行的分子设计策略。