Evaluation of cytotoxic properties of two fluorescent fac-Re(CO)3 complexes bearing an N,N-bidentate benzimidazole coligand.

The reaction between 1H-benzimidazol-2-ylmethyl-(N-aryl)amine derivatives (LR) and [ReBr(CO)5] afforded octahedral Re(i) complexes of the general formula of [ReBr(CO)3LR] (R = 4-Cl and 4-COOCH3). The Re(i) complexes were screened for their potential cytotoxicity against three malignant cell lines and one normal cell line of different origins. The solvatochromic characteristics of the complexes were examined by UV/vis. spectroscopy with the aid of time-dependent density functional theory calculations. Strong autofluorescence emission can be seen in the two Re(i) complexes between 460 and 488 nm. They appeared to accumulate inside intercellular connections and surrounding cellular membranes. The substances gathered also, along the cell membrane, waiting for their entry. The mode of cell death staining and the DNA fragmentation analysis revealed that the 4-Cl complex showed increased apoptotic changes in the MCF-7, and the Caco-2 cell line, while the HepG2 cell line showed little apoptotic changes.

Light-activated cytotoxicity of dicarbonyl Ru(II) complexes with a benzimidazole coligand towards breast cancer.

Reaction between [RuCl2(CO)2]n and 1H-benzimidazol-2-ylmethyl-(N-phenyl)amine ligands (LR) functionalized with various electron-donating and electron-withdrawing substituents on the phenyl ring (R = H, 4-CH3, 4-Cl, 4-COOCH3, and 3-COOCH3) afforded the dark-stable photoactivatable carbon monoxide prodrugs of the general formula [RuCl2(CO)2LR]. Release of the CO molecules from the Ru(II) compounds was examined by monitoring the electronic and IR spectra upon illumination at 365 nm. A noticeable decrease in the intensities of the two characteristic ν(CO) modes for Ru(CO)II2 species, and the growth of two new bands for the mono-carbonyl species and free CO, were the main features of the photolysis profiles. The cytotoxicity of the complexes towards breast cancer (MCF-7) cells was assessed with and without illumination at 365 nm. All the complexes except that with a 4-COOCH3 group (IC50 = 45.08 ± 3.5 µM) are nontoxic under dark conditions. Upon illumination, all the compounds acquired cytotoxicity in the following order: H > 4-COOCH3 > 4-CH3 > 4-Cl > 3-COOCH3. Investigation of the cytotoxicity of the CO-depleted fragments showed that the light-induced cytotoxicity can be attributed to the liberated CO and CO-depleted metal fragments, including the liberated benzimidazole ligands.