The neutral dinuclear complexes [(η
5-C
5Me
5)
2Rh
2(μ-dhnq)Cl
2] (
1) and [(η
5-C
5Me
5)
2Ir
2(μ-dhnq)Cl
2] (
2) (dhnqH
2 = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η
5-C
5Me
5)M(μ-Cl)Cl]
2 (M = Rh, Ir) with dhnqH
2 in the presence of CH
3COONa. Treatment of
1 or
2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF
3SO
3, affords the corresponding tetranuclear metalla-rectangles [(η
5-C
5Me
5)
4M
4(μ-dhnq)
2(μ-L)
2]
4+ (L = pyrazine, M = Rh,
3; M = Ir,
4;
L = 4,4′-bipyridine, M = Rh,
5; M = Ir,
6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh,
7; M = Ir,
8). All complexes were isolated as their triflate salts and were fully characterized by infrared,
1H and
13C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of
3,
5 and
6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes
5 and
6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles
3–
8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC
50 values in the low micromolar range.
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