Single-Pot Self-Assembly of Heteroleptic Mn(I)-Based Aminoquinonato-Bridged Ester/Amide-Functionalized Dinuclear Metallastirrups: Potential Anticancer and Visible-Light-Triggered CORMs.

Abstract

Multicomponent self-assembly of Mn2(CO)10, a bis-chelating aminoquinonato (ON∩ON) bridge (L), and an ester/amide-functionalized flexible neutral ditopic linker (L′) has resulted into the formation of M2LL′-type manganese(I)-based dinuclear metallastirrups of general formula [{(CO)3Mn(μ-η4-L)Mn(CO)3}(μ-L′)] (1–10). Compounds 1–10 were accomplished via orthogonal bonding of the aminoquinone ligand (2,5-bis(n-butylamino)-1,4-benzoquinone/2,5-bis(phenethylamino)-1,4-benzoquinone) and ditopic pyridyl ligand to manganese carbonyl. The resultant metallastirrups were characterized using elemental analyses and IR, UV–vis, 1H NMR, and electrospray ionization-mass spectroscopic techniques. The molecular structure of 6 was confirmed by single-crystal X-ray diffraction methods. Furthermore, molecular recognition capabilities of 1, 5, 7, and 9 were evaluated with aromatic compounds containing hydroxy/amine functionalities. Anticancer activities of compounds 1−3, 5−7, 9, and 10 were investigated against three cancer cell lines, that is, lung (A549), colon (HCT-15), and cervical (HeLa) as well as on normal cells (HEK 293). Compound 9 showed a broad-spectrum inhibition toward these cancer cells upon exposure to visible light. The myoglobin assay was performed using UV–vis absorption spectroscopy to investigate the visible-light-triggered CO release from 5 and 9 that could be related to their ability to effectively inhibit cancer cells. In addition, morphological studies confirmed the induction of autophagy due to the treatment of cancer cells using compound 9.