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 Ag10 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 Ag13 icosahedron and an integrated cage‐like organometallic shell with a C3 symmetry, and possesses a superatomic 6‐electron configuration (1S2ǀ1P4). By contrast, R/S‐Ag16, formed in the high‐concentration R/S‐BNP, features a sandwich‐like pentagram with AgI‐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 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.

中文翻译：

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手性配体浓度介导银簇的不对称转变：NIR-II 圆偏振磷光照明

具有圆偏振磷光（CPP）的近红外（NIR）发射器（称为NIR CPP）已成为尖端发光材料研究的关键部分。然而，获得具有近红外 CPP 活性的纳米团簇仍然是一个挑战。在这里，我们提出了一种不对称转化方法，在不同浓度的手性诱导剂（R/S）存在下，使用非手性Ag10纳米团簇作为起始材料，有效合成两对手性银纳米团簇（R/S-Ag29和R/S-Ag16） )-1,1'-联萘-2,2'-二基磷酸氢盐（R/S-BNP）。 R/S-Ag29在低浓度R/S-BNP中形成，表现出独特的核壳结构，由扭曲的Ag13二十面体和具有C3对称性的集成笼状有机金属壳组成，并具有超原子6-电子构型（1S2-1P4）。相比之下，在高浓度 R/S-BNP 中形成的 R/S-Ag16 具有三明治状五角星形和纯 AgI 内核。得益于分级手性结构和超原子核主导的磷光，R/S-Ag29 在第二近红外（975 nm）区域表现出罕见的 CPP 活性，是在 CPL 金属纳米团簇中观察到的第一个 NIR-II CPP 实例。这项研究提出了一种降低手性银纳米材料从头合成难度的新方法，并有助于近红外区域CPP活性超原子纳米团簇的设计。