Creation of Assembled Plasmonic Network Architectures with Selective Capture of Guest Molecules in Hotspots Region

Abstract Plasmonic networks attract increasing attention owing to their strong plasmon coupling effects at hotspot regions, where intriguing, collective optical behavior and field enhancement occur. Engineering network architectures with flexible control over density and intensity of hotspots, thus fine‐tuning electromagnetic field is the prerequisite for fully exploiting their potential use in diverse plasmon‐based applications, but it represents a great challenge. Herein, a cage‐assisted bottom‐up self‐assembly strategy is proposed to construct a series of cage‐bridged complex network architectures with a high degree of flexibility in hotspot modulation. Critical parameters associated with plasmonic networks, including interparticle distance, the density and intensity of hotspots, as well as molecule accessibility of hotspot can be simultaneously and flexibly adjusted at will. Importantly, the integration of host–guest chemistry of molecular cages into interparticle regions of networks endows selective molecule trapping capability in hotspots, offering tremendous opportunities for broader plasmon‐based applications. The present study not only develops efficient plasmonic networks with enhanced density of hotspots and intense electromagnetic fields, but also provides new avenues for artificially engineering network architectures with advanced functionalities and facilitates further applications in sensing and optoelectronics.