Chiral Ligand‐Concentration Mediating Asymmetric Transformations of Silver Nanoclusters: NIR‐II Circularly Polarized Phosphorescence Lighting

Abstract Near infrared (NIR) emitter with circularly polarized phosphorescence (CPP), known as NIR CPP, has emerged as a key part in the research of cutting‐edge luminescent materials. However, it remains a challenge to obtain nanoclusters with NIR CPP activity. Here, we propose an asymmetric transformation approach to efficiently synthesize two pairs of chiral silver nanoclusters ( R/S ‐Ag29 and R/S ‐Ag16 ) using an achiral Ag 10 nanocluster as starting material in the presence of different concentration chiral inducer ( R/S )‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate ( R/S ‐BNP). R/S ‐Ag29 , formed in the low‐concentration R/S ‐BNP, exhibits a unique kernel‐shell structure consisting of a distorted Ag 13 icosahedron and an integrated cage‐like organometallic shell with a C 3 symmetry, and possesses a superatomic 6‐electron configuration (1S 2 |1P 4 ). By contrast, R/S ‐Ag16 , formed in the high‐concentration R/S ‐BNP, features a sandwich‐like pentagram with Ag I ‐pure kernel. Profiting from the hierarchically chiral structures and superatomic kernel‐dominated phosphorescence, R/S ‐Ag29 exhibits infrequent CPP activity in the second near‐infrared (975 nm) region, being the first instance of NIR‐II CPP observed among CPL‐active metal nanoclusters. This study presents a new approach to reduce the difficulty of de novo synthesis for chiral silver nanomaterials, and facilitates the design of CPP‐active superatomic nanoclusters in NIR region.