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The simple but rarely used heterotopic divergent ligand N-oxide-4,4′-bipyridine (bipyMO) has been exploited, for the first time, for the preparation of heterometallic derivatives, showing the ability to selectively use its two potential coordination sites in dependence of the metal ion nature. By reacting in refluxing acetonitrile ∞ 1 [Cu(hfac) 2 (bipyMO)] with ∞ 1 [Mn(hfac) 2 (bipyMO)] (herein completely characterized), the heterometallic self-assembled monodimensional coordination polymer containing the two regularly alternated moieties Cu(hfac) 2 [N] 2 and Mn(hfac) 2 [O] 2 was obtained in high yield and purity and structurally characterized. On the other hand, a molecular heterometallic compound was obtained using, as a ligand, the here prepared mononuclear complex trans -[PtCl 2 (bipyMO)(PPh 3 )], with the hypodentate bipyMO ligand coordinated to platinum through the nitrogen atom. Reaction with [Zn(hfac) 2 (DME)] afforded the heterometallic trinuclear complex trans [Zn(hfac) 2 { trans -PtCl 2 (PPh 3 )(bipyMO)} 2 ] that was structurally characterized. [ABSTRACT FROM AUTHOR]