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Boron complexes of π-extended nitroxide ligands exhibiting three-state redox processes and near-infrared-II (NIR-II) absorption properties.

Persistent radicals have attracted increasing attention owing to their fascinating properties, including multi-step redox and long-wavelength absorption characteristics. In this study, boron complexes with π-extended nitroxide ligands were synthesised via… Click to show full abstract

Persistent radicals have attracted increasing attention owing to their fascinating properties, including multi-step redox and long-wavelength absorption characteristics. In this study, boron complexes with π-extended nitroxide ligands were synthesised via Buchwald-Hartwig amination reactions of the corresponding boron-nitroxide complex and diarylamines. These nitroxide complexes exhibited two-step and reversible one-electron oxidation processes, suggesting stable redox triads involving anionic aminoxide, neutral nitroxide-radical, and cationic oxoammonium ligands. Cationic boron complexes of the nitroxide radical ligands were obtained via chemical oxidation of the aminoxide complexes and structurally characterised. The cationic nitroxide-radical complexes exhibited strong absorptions at approximately 1100 nm, demonstrating their potential as near-infrared (NIR)-II-active functional dyes.

Keywords: nitroxide ligands; near infrared; boron complexes; complexes extended; infrared nir; extended nitroxide

Journal Title: Dalton transactions
Year Published: 2022

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