Solvation‐Mediated Self‐Assembly from Crystals to Helices of Protic Acyclic Carbene AuI‐Enantiomers with Chirality Amplification

Abstract Constructing chiral supramolecular assembly and exploring the underlying mechanism are of great significance in promoting the development of circularly polarized luminescence (CPL)‐active materials. Herein, we report a solvation‐mediated self‐assembly from single‐crystals to helical nanofibers based on the first protic acyclic (methoxy)(amino)carbenes (pAMACs) Au I ‐enantiomers driven by a synergetic aurophilic interactions and H‐bonds. Their aggregation‐dependent thermally activated delayed fluorescence properties with high quantum yields ( Φ FL ) up to 95 % were proved to be attributed to packing modes of Au⋅⋅⋅Au dimers with π‐stacking or one‐dimensional extended Au⋅⋅⋅Au chains. Via drop‐casting method, supramolecular P ‐ or M ‐helices were prepared. Detailed studies on the helices demonstrate that formations of extended helical Au⋅⋅⋅Au molecular chains amplify supramolecular chirality, leading to strong CPL with high dissymmetry factor (| g lum |=0.030, Φ FL =67 %) and high CPL brightness ( B CPL ) of 4.87×10 −3 . Our findings bring new insights into the fabrication of helical structures to improve CPL performance by modifying aurophilic interactions.