Electrochemiluminescent Enantioselective Recognition on Chiral Channel‐Engineered Metal−Organic Framework Nanostructures

Abstract Chiral discrimination by a simple and efficient sensing means is highly desirable but a challenge for the study of chiral compounds. In this work, a chiral metal–organic framework (CMOF) with a tailored channel size is combined for the first time with electrochemiluminescence (ECL) in a synergistic approach to construct a chiral recognition ECL (CR‐ECL) system for efficient discrimination of tryptophan (Trp) enantiomers. Notably, Trp functions dually as both the analyte and the co‐reactant, generating distinct ECL signals in the presence of the luminophore (sodium tetraphenylborate, TPB). The chiral‐functionalized MOF808‐His, with its precisely designed channels and pores, preferentially permits the transport and oxidation of L‐Trp, leading to a significantly stronger luminescence signal compared to D‐Trp. Owing to the enantioselective recognition enabled by the unique chiral channels, a high recognition efficiency is achieved with an ECL intensity ratio (ECL _L /ECL _D ) of 13.4, demonstrating excellent ECL enantioselectivity. This study pioneers a novel strategy for developing CR‐ECL systems based on the channel‐engineered CMOF. It not only offers a simple, rapid, and cost‐effective approach for enantioselective recognition but also innovatively advances the application of channel‐engineered CMOF in chiral discrimination and ECL‐based bioassays.