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

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 λ_max ∼1300 nm and can be either oxidized to regular [M^II (MB-DIPY)]⁺ (M=Cu or Ni) or reduced to [M^II (MB-DIPY)]^- compounds. The radical nature of the stable [M^II (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.