Abstract
The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of “Manitoba dipyrromethenes” (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax∼1300 nm and can be either oxidized to regular [MII(MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII(MB-DIPY)]− compounds. The radical nature of the stable [MII(MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.
Original language | English (US) |
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Article number | e202201181 |
Journal | Chemistry - A European Journal |
Volume | 28 |
Issue number | 41 |
DOIs | |
State | Published - Jul 20 2022 |
Bibliographical note
Publisher Copyright:© 2022 Wiley-VCH GmbH.
Keywords
- aza-BODIPY
- azadipyrromethene
- copper
- near-infrared absorption
- nickel
- stable radicals
PubMed: MeSH publication types
- Journal Article