Li Yawen, Lin Siyi, Zhang Chi, Chen Yi, Zhou Siyuan, Wang Lu, Chen Shigui, Ding Tao
Key Laboratory of Artificial Micro/Nano Structure of Ministry of Education, School of Physics and Technology, Wuhan University, 430072 Wuhan, China.
The Institute for Advanced Studies, Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, Wuhan University, 299 Bayi Road, Wuhan, Hubei 430072, China.
J Am Chem Soc. 2024 Oct 23;146(42):28739-28747. doi: 10.1021/jacs.4c07322. Epub 2024 Oct 9.
Miniaturization and integration of plasmonic nanodevices are fundamentally limited by quantum tunneling, which leads to quantum plasmonics with reduced local E-field intensity. Despite significant efforts devoted to modeling and deterring the detrimental effect of quantum plasmonics, the modulation and application of electron transport through the subnanometer gaps seems rarely exploited due to the limited tunability of conventional quantum materials. Here, we establish a supramolecular plasmonic system made of pillar[5]arene complexes and plasmonic resonators (nanoparticle-on-mirror, NPoM). The supramolecular assemblies significantly enhance the gap conductance of NPoM, which results in a blue-shift of the coupled plasmons. Plasmonic hot-electron transport with laser excitation further modulates the gap plasmons, which are fully reversible and beneficial for enhanced chiroptic sensing. Such a conductive supramolecular plasmonic system not only suggests an optoelectronic switching strategy for charge transfer plasmons but also provides a superior sensing platform for single molecules.
等离子体纳米器件的小型化和集成从根本上受到量子隧穿的限制，这导致了局部电场强度降低的量子等离子体学。尽管人们付出了巨大努力来对量子等离子体学的有害影响进行建模和抑制，但由于传统量子材料的可调性有限，通过亚纳米间隙的电子传输的调制和应用似乎很少被利用。在这里，我们建立了一个由柱[5]芳烃配合物和等离子体谐振器（纳米颗粒-镜面，NPoM）组成的超分子等离子体系统。超分子组装显著提高了NPoM的间隙电导，这导致耦合等离子体的蓝移。激光激发下的等离子体热电子传输进一步调制间隙等离子体，这是完全可逆的，并且有利于增强手性传感。这种导电超分子等离子体系统不仅为电荷转移等离子体提出了一种光电开关策略，而且为单分子提供了一个优越的传感平台。
