Tian Li, Wang Chen, Zhao Hongwei, Sun Fuwei, Dong Hao, Feng Kai, Wang Peng, He Guokang, Li Guangtao
Department of Chemistry, Key Lab of Organic Optoelectronics & Molecular Engineering, Tsinghua University, Beijing 100084, China.
Institute of Chemistry, Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
J Am Chem Soc. 2021 Jun 16;143(23):8631-8638. doi: 10.1021/jacs.0c13377. Epub 2021 Jun 2.
Plasmonic dimers not only provide a unique platform for studying fundamental plasmonic behavior and effects but also are functional materials for numerous applications. The efficient creation of well-defined dimers with flexible control of structure parameters and thus tunable optical property is the prerequisite for fully exploiting the potential of this nanostructure. Herein, based on a polymer-assisted self-assembly approach in conjugation with molecular cage chemistry, a strategy was demonstrated for constructing cage-bridged plasmonic dimers with controlled sizes, compositions, shape, symmetry, and interparticle gap separation in a modular and high-yield manner. With a high degree of freedom and controllability, this strategy allows facilely accessing various symmetrical/asymmetrical dimers with sub-5 nm gap distance and tailored optical properties. Importantly, as the linkage of the two constituent elements, the molecular cages embedded in the junction endow the assembled dimers with the ability to precisely and reversibly host rich guest molecules in hotspot regions, offering great potential for creating various plasmon-mediated applications.
等离子体二聚体不仅为研究基本的等离子体行为和效应提供了一个独特的平台，而且是用于众多应用的功能材料。高效创建具有结构参数灵活控制从而具有可调光学性质的明确二聚体，是充分挖掘这种纳米结构潜力的先决条件。在此，基于聚合物辅助自组装方法并结合分子笼化学，展示了一种策略，用于以模块化和高产率的方式构建具有可控尺寸、组成、形状、对称性和粒子间间隙间距的笼桥连等离子体二聚体。该策略具有高度的自由度和可控性，能够轻松获得间隙距离小于5 nm且具有定制光学性质的各种对称/不对称二聚体。重要的是，作为两个组成元素的连接体，嵌入连接处的分子笼赋予组装好的二聚体在热点区域精确且可逆地容纳丰富客体分子的能力，为创建各种等离子体介导的应用提供了巨大潜力。
