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
复制标题
镍 (II)/铜 (II) 和氧化还原非无害 MB-DIPY 配体的自由基配合物：异常的稳定性和强近红外吸收（在 最大 ≤1300 nm 处）
DOI：
10.1002/chem.202201181
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Nemykin, Victor N.
中科院分区：
文献类型：
--
作者：
Zatsikha, Yuriy V.;Shamova, Liliya I.;Shepit, Michael;Berry, Steven M.;Thomas, Fabrice;Herbert, David E.;van Lierop, Johan;Nemykin, Victor N.
制备具有1000 nm以上强吸收和氧化还原可切换吸收的自由基是功能染料化学中的一个长期挑战。本文报道了一系列前所未有的稳定的中性镍(II)、铜(II)“马尼托巴二吡咯亚甲基”(MB-DIPY)配合物的制备。新的稳定自由基在λmax∼1300 nm处有较强的吸收，可被氧化为规则的[MII(MB-DIPY)]+(M=铜或镍)或还原为[MII(MB-DIPY)]−化合物。稳定的[MII(MB-DIPY)]络合物的自由基性质通过EPR光谱得到证实，并通过UV-Vis光谱、电化学和光谱电化学、磁性测量和X射线结晶学获得了更多的电子结构。用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)研究了自由基发色团的电子结构和光谱性质。这些镍(II)和铜(II)络合物是第一个具有MB-DIPY配体的稳定自由基化合物。
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 atλmax∼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.