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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
Authors:Dr Yuriy V Zatsikha  Dr Liliya I Shamova  Michael Shepit  Steven M Berry  Prof Dr Fabrice Thomas  Prof Dr David E Herbert  Prof Dr Johan van Lierop  Prof Dr Victor N Nemykin
Institution:1. Department of Chemistry, University of Manitoba, Winnipeg MB, R3T 2 N2 Canada;2. Department of Physics and Astronomy, University of Manitoba, Winnipeg MB, R3T 2 N2 Canada;3. Department of Chemistry and Biochemistry, University of Minnesota–Duluth, Duluth, MN 55812 USA;4. Univ. Grenoble Alpes, CNRS, DCM, 38000 Grenoble, France
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.
Keywords:aza-BODIPY  azadipyrromethene  copper  near-infrared absorption  nickel  stable radicals
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