Ru(II) Oligothienyl Complexes with Fluorinated Ligands: Photophysical, Electrochemical, and Photobiological Properties

被引：11
作者：
Cole, Houston D. [1 ]
Vali, Abbas [1 ]
Roque III, John A. [1 ]
Shi, Ge [1 ]
Talgatov, Alisher [1 ]
Kaur, Gurleen [1 ]
Frances-Monerris, Antonio [2 ]
Alberto, Marta E. [3 ]
Cameron, Colin G. [1 ]
McFarland, Sherri A. [1 ]
机构：
[1] Univ Texas Arlington, Dept Chem & Biochem, Arlington, TX 76019 USA
[2] Univ Valencia, Inst Ciencia Mol, Valencia 46071, Spain
[3] Univ Calabria, Dipartimento Chim & Tecnol Chim, I-87036 Arcavacata Di Rende, Italy
来源：
INORGANIC CHEMISTRY | 2024年 / 63卷 / 21期
基金：
美国国家卫生研究院; 美国国家科学基金会;
关键词：
PHOTODYNAMIC THERAPY; ANTITUMOR IMMUNITY; 2,2-BIPYRIDINE COMPLEXES; THEORETICAL EXPLORATION; RUTHENIUM(II) COMPLEXES; ALPHA-OLIGOTHIOPHENES; POLYPYRIDYL COMPLEXES; THIOETHER LIGAND; EXCITED-STATES; IMMUNOTHERAPY;
D O I：
10.1021/acs.inorgchem.3c04382
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A series of Ru(II) complexes incorporating two 4,4 '-bis(trifluoromethyl)-2,2 '-bipyridine (4,4 '-btfmb) coligands and thienyl-appended imidazo[4,5-f][1,10]phenanthroline (IP-nT) ligands was characterized and assessed for phototherapy effects toward cancer cells. The [Ru(4,4 '-btfmb)(2)(IP-nT)](2+) scaffold has greater overall redox activity compared to Ru(II) polypyridyl complexes such as [Ru(bpy)(3)](2+). Ru-1T-Ru-4T have additional oxidations due to the nT group and additional reductions due to the 4,4 '-btfmb ligands. Ru-2T-Ru-4T also exhibit nT-based reductions. Ru-4T exhibits two oxidations and eight reductions within the potential window of -3 to +1.5 V. The lowest-lying triplets (T-1) for Ru-0T-2T are metal-to-ligand charge-transfer ((MLCT)-M-3) excited states with lifetimes around 1 mu s, whereas T-1 for Ru-3T-4T is longer-lived (similar to 20-24 mu s) and of significant intraligand charge-transfer ((ILCT)-I-3) character. Phototoxicity toward melanoma cells (SK-MEL-28) increases with n, with Ru-4T having a visible EC50 value as low as 9 nM and PI as large as 12,000. Ru-3T and Ru-4T retain some of this activity in hypoxia, where Ru-4T has a visible EC50 as low as 35 nM and PI as high as 2900. Activity over six biological replicates is consistent and within an order of magnitude. These results demonstrate the importance of lowest-lying (ILCT)-I-3 states for phototoxicity and maintaining activity in hypoxia.
引用
收藏
页码：9735 / 9752
页数：18
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