Materials with circularly polarized luminescence (CPL) are especially fascinating due to the widespread potential applications in 3D displays, biological probes, security encoding, encrypted information transmission, and storage. Among these CPL‐active materials, the ones based on atomically precise coinage, namely, the metal coinage clusters, have attracted increasing attention due to their fascinating chiral structures and intriguing luminescence characteristics. Meanwhile, these clusters provide an ideal platform at the nanoscale for understanding the chiral transfer across the organic–inorganic interface. In this report, the recent progress in constructing enantiomerically pure chiral coinage metal clusters and the luminescent mechanism of coinage metal clusters in aggregated state are reviewed, respectively. Moreover, CPL‐active atomically precise coinage metal clusters and their design strategies are discussed in detail. Finally, challenges and opportunities for constructing atomically precise coinage metal clusters with excellent CPL properties are discussed.
Atomically precise enantiomeric metal clusters are scarce, and copper(I) alkynyl clusters with intense circularly polarized luminescence (CPL) responses have not been reported. A pair of chiral alkynyl ligands, (R/S)‐2‐diphenyl‐2‐hydroxylmethylpyrrolidine‐1‐propyne (abbreviated as R/S‐DPM) we successfully prepared and single crystals were characterized of optically pure enantiomeric pair of atomically‐precise copper(I) clusters, [Cu14(R/S‐DPM)8](PF6)6 (denoted as R/S‐Cu14), which feature bright red luminescence and CPL with a high luminescence anisotropy factor (glum). A dilute solution containing R/S‐Cu14 was nonluminescent and CPL inactive at room temperature. Crystallization‐ and aggregation‐induced emission (CIE and AIE, respectively) contribute to the triggering of the CPL of R/S‐Cu14 in the crystalline and aggregated states. Their AIE behavior and good biocompatibility indicated applications of these copper(I) clusters in cell imaging in HeLa and NG108‐15 cells.
Facile preparation of metal‐free materials as efficient, stable and economical catalysts for oxygen reduction reaction (ORR) is highly desirable but remains challenging for metal‐air battery and fuel cell applications. Herein, firstly through pyrolysing tea dregs with inorganic salts, we developed a simple approach to synthesize a heteroatoms quaternary‐doped (B, N, P, S) porous carbon as a new metal‐free ORR catalyst. Remarkably, after doping with heteroatoms, such prepared hybrid material displays significantly higher onset potential and limiting diffusion current density than the corresponding undoped carbon with similar specific surface area, and much better stability than commercial Pt/C catalyst in alkaline and even neutral solutions. Notably, when used in a Zn–air battery, our hybrid catalyst can reveal comparable open circuit voltage and power density, but better stability than these of Pt/C catalyst as well.
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