Synthesis of mono-nitroxides and of bis-nitroxides with varying electronic through-bond communication

Angeliki Giannoulis*, Katrin Ackermann, Alexey Bogdanov, David B. Cordes, Catherine Higgins, Joshua Ward, Alexandra M. Z. Slawin, James E. Taylor*, Bela E. Bode*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Nitroxides are a unique class of persistent radicals finding a wide range of applications, from spin probes to polarizing agents, and recently bis-nitroxides have been used as proof-of-concept molecules for quantum information processing. Here we present the syntheses of pyrroline-based nitroxide (NO) radicals and give a comparision of two possible synthetic routes to form two key intermediates, namely 2,2,5,5-tetramethylpyrroline-1-oxyl-3-acetylene (TPA) and 1-oxyl-2,2,5,5-tetramethylpyrroline-3-carboxylic acid (TPC). TPC and TPA were then used as precursors for the synthesis of three model compounds featuring two distant NO groups with a variable degree of conjugation and thus electronic communication between them. Using relatively facile synthetic routes, we produced a number of mono- and bis-nitroxides with the structures of multiple compounds unambiguously characterized by X-ray crystallography, while Continuous Wave Electron Paramagnetic Resonance (CW-EPR) allowed us quantify the electronic communication in the bis-nitroxides. Our study expands the repertoire of mono- and bis-nitroxides with possibilities of exploiting them for studying quantum coherence effects and as polarizing agents.
Original languageEnglish
Pages (from-to)375-385
Number of pages11
JournalOrganic & Biomolecular Chemistry
Issue number2
Early online date8 Dec 2022
Publication statusPublished - 14 Jan 2023


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