Tunable Macrocyclic Polyparaphenylene Nanolassos via Copper-Free Click Chemistry.

Abstract

Deriving diverse compound libraries from a single substrate in high yields remains to be a challenge in cycloparaphenylene chemistry. In here, a strategy for the late-stage functionalization of shape-persistent alkyne-containing cycloparaphenylene has been explored using readily available azides. The copper-free [3+2]azide-alkyne cycloaddition provided high yields (>90 %) in a single reaction step. Systematic variation of the azides from electron-rich to -deficient shines light on how peripheral substitution influences the characteristics of the resulting adducts. We find that among the most affected properties are the molecular shape, the oxidation potential, excited-state features, and affinities towards different fullerenes. Joint experimental and theoretical results are presented including calculations with the state-of-the-art, artificial intelligence-enhanced quantum mechanical method 1 (AIQM1).