Multicomponent Self-Assembly of Diaminobenzoquinonato-Bridged Manganese(I) Metallosupramolecular Rectangles: Host-Guest Interactions, Anticancer Activity, and Visible-Light-Induced CO Releasing Studies.

The one-pot self-assembly of Mn2(CO)10, a bis-chelated diaminobenzoquinonato (ON∩ON) bridge (L), and a linear ditopic linker (N∩N) (L') has resulted into the formation of M4L2L2'-type manganese(I)-based tetranuclear metallorectangles of the general formula [{(CO)3Mn(µ-η4-L)Mn(CO)3}2(µ-(N-N)2)] (1-8), wherein L is 2,5-bis(n-butylamine)-1,4-benzoquinone (bbbq) and/or 2,5-bis(phenethylamino)-1,4-benzoquinone (bpbq) and N-N is 4,4'-bipyridine (bpy), trans-1,2-bis(4-pyridyl) ethylene (bpe), phenyl-1,4-bis(isonicotinate) (pbin), and N,N'-bis(4-pyridylformamide)-1,4-benzene (bpfb). Metallorectangles 1-8 were characterized by infrared, ultraviolet-visible (UV-vis) absorption, and 1H nuclear magnetic resonance spectroscopies, elemental analysis, and electrospray ionization-mass spectrometry. The molecular and crystal structures of 1•n(CHCl3) and coronene⊂3•coronene were determined by the single-crystal X-ray diffraction method. Host-guest binding abilities of 1, 3, and 7 with coronene, pyrene, and 4,4'-dihydroxybiphenyl were investigated using UV-vis absorption and emission spectroscopic techniques. Formation of host-guest complexes was further confirmed by the single-crystal X-ray structural analysis. Absorption of spectra of these metallorectangles showed high-intensity metal-ligand charge transfer as a broad band in the visible region. In vitro cytotoxicity assays were performed on 1, 3, 5, and 7 against lung, colon, and cervical cancer cells as well as normal cells. Compounds 5 and 7 were identified as visible-light-induced CO-releasing molecules from the myoglobin assay.

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

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.