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This work provides a foundation for further exploration of the [4 + 2]-cycloaddition reaction and future customization of pyridine-containing macrocyclic peptides.The urgent demand for high energy and safety storage devices is pushing the development of lithium metal batteries. However, unstable solid electrolyte interface (SEI) formation and uncontrollable lithium dendrite growth are still huge challenges for the practical use of lithium metal batteries. Herein, a composite polymer electrolyte (CPE) endowed with designated ion channels