Synthesis and complexes of a constrained-cavity Schiff-base dipyrrin macrocycle

The preparation of radicals with intense and redoxswitchable 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)] À 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.The preparation of radicals with intense absorption in the nearinfrared (NIR) region (λ max > 1000 nm) that are stable under ambient conditions is a very challenging task. It is even more challenging to create radical systems with prominent and reversible electro-or chemochromic properties with an organic chromophore in its radical-anion state. BODIPYs and aza-BODIPYs are highly popular as fluorescent markers and biomarkers, fluorescent sensors, NIR dyes, PDT agents, light-[a] Dr.

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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 λ_max ∼1300 nm

Zatsikha

Shamova

Shepit

et al. 2022

Chemistry A European J

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Direct Synthesis of ABCD‐Porphyrin Platinum(II) Complexes via Dehydrative Aromatization

Inoue

Yokoyama

Maruyama

et al. 2023

Chemistry A European J

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Since the development of the first method for porphyrin synthesis by Rothemund in 1935, porphyrin derivatives have been widely investigated and have played an essential role in chemical sciences. Most synthetic routes of porphyrins involve oxidative aromatization. Herein, we present a synthetic method to produce ABCD‐porphyrins, including chiral ones, through a one‐pot reaction involving “coordination, cyclization, and dehydrative aromatization” using a mono‐dipyrrinatoPt(II)Cl(COE) (COE = cyclooctene) complex as a platinum template.

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Observation of a 3-in-1 Russian-doll-like Complex in Solution

Jiang

2021

Chem. Res. Chin. Univ.

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Synthesis and complexes of a constrained-cavity Schiff-base dipyrrin macrocycle

Abstract: A one-pot cyclisation/oxidation process results in a new constrained-cavity Schiff-base dipyrrin macrocycle and allows access to Li, Fe, and Zn complexes of this unique chromophore.

Cited by 6 publications

References 44 publications

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

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

Direct Synthesis of ABCD‐Porphyrin Platinum(II) Complexes via Dehydrative Aromatization

Observation of a 3-in-1 Russian-doll-like Complex in Solution

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Synthesis and complexes of a constrained-cavity Schiff-base dipyrrin macrocycle

Abstract: A one-pot cyclisation/oxidation process results in a new constrained-cavity Schiff-base dipyrrin macrocycle and allows access to Li, Fe, and Zn complexes of this unique chromophore.

Cited by 6 publications

References 44 publications

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

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

Direct Synthesis of ABCD‐Porphyrin Platinum(II) Complexes via Dehydrative Aromatization

Observation of a 3-in-1 Russian-doll-like Complex in Solution

Contact Info

Product

Resources

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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 λ_max ∼1300 nm

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