Indian Institute of Technology Gandhinagar, Palaj Campus, Gandhinagar, Gujarat-382355, India.
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore-560012, India.
Dalton Trans. 2022 Mar 8;51(10):3849-3863. doi: 10.1039/d1dt04218a.
A series of luminescent Ir(III) dipyrrinato complexes were synthesized having various aromatic chromophores at the C-5 position of dipyrrin ligands. The presence of different chromophores on the Ir(III) dipyrrinato complexes altered their optical properties and produced strong emission in the red to NIR region (680-900 nm) with huge Stokes shifts (5910-7045 cm). TD-DFT studies indicated significant charge distribution between dipyrrin ligands and Ir-cyclometalated units in all the molecules. X-ray crystal structures revealed an octahedral geometry of the Ir(III) center in the complex. The studies of the glycosylated Ir(III) complexes revealed strong photoluminescence with maximum Stokes shifts, and they showed significant photocytotoxicity in skin keratinocyte (HaCaT) and lung adenocarcinoma (A549) cells. The singlet oxygen generation quantum yields of glycosylated Ir(III) complexes were in the range of 70-78% in water. The estimated IC values were between 17 and 25 μM after light exposure, and confocal microscopy revealed significant localization of the glycosylated Ir(III) complexes in the endoplasmic reticulum (ER) of cancer cells. The neutral Ir(III) dipyrrinato complexes are promising tracking agents for cellular imaging in the biological window and for photodynamic therapy (PDT) applications.
一系列具有不同芳香发色团的发光铱（III）二吡咯甲川配合物被合成，这些发色团位于二吡咯配体的 C-5 位。铱（III）二吡咯甲川配合物上不同发色团的存在改变了它们的光学性质，并在红色到近红外区域（680-900nm）产生强烈的发射，具有巨大的斯托克斯位移（5910-7045cm）。TD-DFT 研究表明，所有分子中都存在二吡咯配体和 Ir-环金属化单元之间的显著电荷分布。X 射线晶体结构揭示了配合物中 Ir（III）中心的八面体几何形状。糖基化铱（III）配合物的研究表明，它们在皮肤角质形成细胞（HaCaT）和肺腺癌细胞（A549）中具有强烈的光致发光和显著的光细胞毒性。糖基化铱（III）配合物的单线态氧生成量子产率在水中的范围为 70-78%。在光暴露后，估计的 IC 值在 17 到 25μM 之间，共聚焦显微镜显示糖基化铱（III）配合物在癌细胞的内质网（ER）中具有显著的定位。中性铱（III）二吡咯甲川配合物是生物窗口中细胞成像和光动力疗法（PDT）应用的有前途的追踪剂。
