Unlocking the Potential of Ru(II) Dual-action Compounds with the Power of the Heavy-atom Effect.
Unlocking the Potential of Ru(II) Dual-action Compounds with the Power of the Heavy-atom Effect.
复制标题
利用重原子效应的力量释放 Ru(II) 双重作用化合物的潜力。
DOI：
10.1111/php.13573
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发表时间：
2022
影响因子：
3.3
通讯作者：
Kodanko,JeremyJ
中科院分区：
文献类型：
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作者：
Toupin,NicholasP;Steinke,SeanJ;Herroon,MackenzieK;Podgorski,Izabela;Turro,Claudia;Kodanko,JeremyJ
本文报道了两个新的钌（II）光活化配合物[Ru（tpy）（Me 2bpy）（L）]2+（tpy = 2，2 '：6'，2“-三联吡啶，Me 2bpy = 6，6 '-二甲基-2，2'-联吡啶）的合成、光化学和生物学性质。制备了两个pyBOD配体，它们带有侧翼的氢或碘原子。Ru（II）结合的BODIPY染料相对于游离染料显示出吸收最大值的红移，并且在绿色光照射下发生BODIPY配体的光解离。将碘添加到BODIPY配体中促进系统间交叉，这导致在游离染料中有效的单线态氧产生，但也提高了从Ru（II）释放BODIPY配体的量子产率。这代表了通过Ru（II）络合物中的重原子效应来增强光解离量子产率的策略的第一份报告。此外，Ru（II）结合的BODIPY染料一旦释放就显示出荧光开启，其中铅类似物显示出针对三阴性乳腺癌细胞的纳摩尔EC 50值，在绿色光照射下>100倍的光疗指数，以及与相应的游离BODIPY光敏剂相比，与正常细胞相比，对癌细胞的选择性更高。传统的钌（II）光活化配合物需要nonbiorthogonal蓝光激活，很少显示亚微摩尔的效力，实现细胞死亡。我们的研究代表了未来Ru（II）配合物的光化学和效能的改善途径。
We report the synthesis, photochemical and biological characterization of two new Ru(II) photoactivated complexes based on [Ru(tpy)(Me2bpy)(L)]2+(tpy = 2,2':6',2''‐terpyridine, Me2bpy = 6,6'‐dimethyl‐2,2'‐bipyridine), where L = pyridyl‐BODIPY (pyBOD). Two pyBOD ligands were prepared bearing flanking hydrogen or iodine atoms. Ru(II)‐bound BODIPY dyes show a red‐shift of absorption maxima relative to the free dyes and undergo photodissociation of BODIPY ligands with green light irradiation. Addition of iodine into the BODIPY ligand facilitates intersystem crossing, which leads to efficient singlet oxygen production in the free dye, but also enhances quantum yield of release of the BODIPY ligand from Ru(II). This represents the first report of a strategy to enhance photodissociation quantum yields through the heavy‐atom effect in Ru(II) complexes. Furthermore, Ru(II)‐bound BODIPY dyes display fluorescence turn‐on once released, with a lead analog showing nanomolar EC50values against triple negative breast cancer cells, >100‐fold phototherapeutic indexes under green light irradiation, and higher selectivity toward cancer cells as compared to normal cells than the corresponding free BODIPY photosensitizer. Conventional Ru(II) photoactivated complexes require nonbiorthogonal blue light for activation and rarely show submicromolar potency to achieve cell death. Our study represents an avenue for the improved photochemistry and potency of future Ru(II) complexes.