Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300 nm

Yuriy V. Zatsikha, Liliya I. Shamova, Michael Shepit, Steven M. Berry, Fabrice Thomas, David E. Herbert, Johan van Lierop, Victor N. Nemykin

Research output: Contribution to journalArticlepeer-review

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 languageEnglish (US)
Article numbere202201181
JournalChemistry - A European Journal
Volume28
Issue number41
DOIs
StatePublished - Jul 20 2022

Bibliographical note

Funding Information:
Generous support by the NSF (CHE‐2153081), Minnesota Supercomputing Institute, University of Tennessee, and Canada WestGrid supercomputing facility to V.N.N. is greatly appreciated. We would like to acknowledge the help of Dr. Tanner Blessener and Dustin Nevonen with some of the data collection. M.S. and J.v.L. acknowledge funding from the Natural Sciences and Engineering Research Council of Canada (CGS−D program, and RGPIN‐2018‐05012) and the Canada Foundation for Innovation.

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

Keywords

  • aza-BODIPY
  • azadipyrromethene
  • copper
  • near-infrared absorption
  • nickel
  • stable radicals

PubMed: MeSH publication types

  • Journal Article

Fingerprint

Dive into the research topics of 'Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300 nm'. Together they form a unique fingerprint.

Cite this