近日，中国科学院福建物质结构研究所林启普团队研究了含荧光团包埋的手性Tin-Oxo簇基用于多色圆偏振发光。2025年7月15日，《德国应用化学》杂志发表了这一成果。

锡氧合金是由锡氧化物核和表面配体组成的多金属聚集体，具有明确的化学成分和结构。手性是控制生物识别和信号转导的基本特征，与广泛研究的贵金属晶体相比，在锡酸盐晶体中仍未得到充分研究。

研究组以轴手性1,1'；-联萘酚（BINOL）配体为主题，构建了3对手性锡氧化合物对映体。结构分析揭示了定向C-H··p相互作用介导的超分子螺旋组装，而圆二色性（CD）光谱证实了其固有手性。通过原位掺杂工程，他们在手性晶体结晶过程中加入具有不同发射谱线的非手性荧光团，制备出具有圆偏振发光（CPL）的复合材料。优化后的系统最大不对称系数（g_lum）为1.5 × 10^-2。机理研究表明，锡氧薄膜的螺旋填料通过空间约束效应促进了立体化学信息向染料的传递。这种超分子手性诱导模式为多功能光学材料的合理设计提供了新的见解。

附：英文原文

Title: Chiral Tin-Oxo Cluster Matrices with Fluorophore Embedment  for Multichromatic Circularly Polarized Luminescence

Author: Gui-Xin Yan, Er-Xia Chen, Jin-Xia Yang, Jian Zhang, Qipu Lin

Issue&Volume: 2025-07-15

Abstract: Tin-oxo clusters, characterized by their well-defined chemical compositions and architectures, are multi-metal aggregates composed of Sn-oxide cores and surface ligands. Chirality, a fundamental characteristic governing biological recognition and signal transduction, remains underexplored in stannate clusters compared to extensively studied precious metal clusters. Herein, three enantiomeric pairs of chiral tin-oxo clusters were constructed using axially chiral 1,1'-binaphthol (BINOL) ligands. Structural analyses revealed supramolecular helical assemblies mediated by directional C-H···p interactions, while circular dichroism (CD) spectroscopy confirmed their intrinsic chirality. Through an in-situ doping engineering, non-chiral fluorophores with distinct emission profiles were incorporated during chiral cluster crystallization, yielding composite materials exhibiting circularly polarized luminescence (CPL). The optimized system achieved a maximum dissymmetry factor (glum) of 1.5 × 10-2.  Mechanistic studies established that the spiral packing of the tin-oxo clusters facilitates stereochemical information transfer to the dyes via spatial confinement effect. This supramolecular chirality induction paradigm offers new insights into the rational design of multifunctional optical materials.

DOI: 10.1002/anie.202509996

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202509996