Extreme Stabilization and Redox Switching of Organic Anions and Radical Anions by Large-Cavity, CH Hydrogen-Bonding Cyanostar Macrocycles

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© 2016 American Chemical Society. Encapsulation of unstable guests is a powerful way to enhance their stability. The lifetimes of organic anions and their radicals produced by reduction are typically short on account of reactivity with oxygen while their larger sizes preclude use of traditional anion receptors. Here we demonstrate the encapsulation and noncovalent stabilization of organic radical anions by C-H hydrogen bonding in π-stacked pairs of cyanostar macrocycles having large cavities. Using electrogenerated tetrazine radical anions, we observe significant extension of their lifetimes, facile molecular switching, and extremely large stabilization energies. The guests form threaded pseudorotaxanes. Complexation extends the radical lifetimes from 2 h to over 20 days without altering its electronic structure. Electrochemical studies show tetrazines thread inside a pair of cyanostar macrocycles following voltage-driven reduction (+e-) of the tetrazine at -1.00 V and that the complex disassembles after reoxidation (-e-) at -0.05 V. This reoxidation is shifted 830 mV relative to the free tetrazine radical indicating it is stabilized by an unexpectedly large -80 kJ mol-1. The stabilization is general as shown using a dithiadiazolyl anion. This finding opens up a new approach to capturing and studying unstable anions and a radical anions when encapsulated by size-complementary anion receptors.

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Journal of the American Chemical Society

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