Metallo‐Supramolecular Helicates as Surface‐Enhanced Raman Scattering (SERS) Substrates with High Tailorability
Bo Song, Zhonghui Zhang, Wei‐Tao Dou, Xiao‐Li Zhao, Yanfei Niu, Chen Wang, Chunchun Li, Jonathan R. Nitschke, Yang Tian, Hai‐Bo Yang, Lin Xu
Abstract
Abstract The exploration of novel functionalized supramolecular coordination complexes (SCCs) can enable new applications in domains that include purification and sensing. In this study, employing a coordination‐driven self‐assembly strategy, we designed and prepared a series of benzochalcogenodiazole‐based metallohelicates as high‐efficiency charge‐transfer surface‐enhanced Raman scattering (SERS) substrates, expanding the range of applications for these metallohelicates. Through structural modifications, including the substitution of single heteroatoms on ligands, replacement of coordinating metals, and alteration of ligand framework linkages, the Raman performance of these metallohelicates as substrates were systematically optimized. Notably, the SERS enhancement factors (EFs) of the metallohelicate‐based SERS substrates were significantly enhanced to levels as high as 1.03×10 7 , which rivals the EFs of noble metals devoid of “hot spots”. Additionally, the underlying Raman enhancement mechanisms of these metallohelicates have been investigated through a combination of control experiments and theoretical calculations. This study not only demonstrates the utility of metallohelicates as SERS substrates but also offers insights and materials for the development of high‐efficiency new charge‐transfer SERS substrates.