Department of Chemistry, Acadia University, Wolfville, NS, Canada.
Department of Chemistry, Brooklyn College of the City University of New York, Brooklyn, NY.
Photochem Photobiol. 2020 Mar;96(2):349-357. doi: 10.1111/php.13177. Epub 2020 Jan 9.
Ru(II) complexes were synthesized with π-expanding (phenyl, fluorenyl, phenanthrenyl, naphthalen-1-yl, naphthalene-2-yl, anthryl and pyrenyl groups) attached at a 1H-imidazo[4,5-f][1,10]phenanthroline ligand and 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmb) coligands. These Ru(II) complexes were characterized by 1D and 2D NMR, and mass spectroscopy, and studied for visible light and dark toxicity to human malignant melanoma SK-MEL-28 cells. In the SK-MEL-28 cells, the Ru(II) complexes are highly phototoxic (EC = 0.2-0.5 µm) and have low dark toxicity (EC = 58-230 µm). The highest phototherapeutic index (PI) of the series was found with the Ru(II) complex bearing the 2-(pyren-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand. This high PI is in part attributed to the π-rich character added by the pyrenyl group, and a possible low-lying and longer-lived IL state due to equilibration with the MLCT state. While this pyrenyl Ru(II) complex possessed a relatively high quantum yield for singlet oxygen formation (Φ = 0.84), contributions from type-I processes (oxygen radicals and radical ions) are competitive with the type-II ( O ) process based on effects of added sodium azide and solvent deuteration.
合成了一系列钌（II）配合物，这些配合物的配体为 1H-咪唑并[4,5-f][1,10]菲咯啉（1H-imidazo[4,5-f][1,10]phenanthroline ligand），连接有一个π-扩展（苯基、芴基、菲基、萘-1-基、萘-2-基、蒽基和芘基）基团，以及 4,4'-二甲氧基-2,2'-联吡啶（4,4'-dmb）共配体。这些 Ru(II) 配合物通过一维和二维 NMR 以及质谱进行了表征，并研究了它们对人恶性黑色素瘤 SK-MEL-28 细胞的可见光和暗毒性。在 SK-MEL-28 细胞中，这些 Ru(II) 配合物具有高的光毒性（EC = 0.2-0.5 μm）和低的暗毒性（EC = 58-230 μm）。该系列中最高的光治疗指数（PI）是由带有 2-(芘-1-基)-1H-咪唑并[4,5-f][1,10]菲咯啉配体的 Ru(II) 配合物产生的。这种高 PI 部分归因于芘基增加的富π特征，以及由于与 MLCT 态平衡而可能存在的低能和长寿命的 IL 态。虽然这个芘基 Ru(II) 配合物具有相对较高的单线态氧生成量子产率（Φ = 0.84），但基于添加的叠氮化钠和溶剂氘化的影响，来自 I 型过程（氧自由基和自由基离子）的贡献与 II 型（ O ）过程竞争。
