The syntheses, structures, and magnetic properties of three new coordination complexes, tetranuclear [Zn2L3(OAc)-(OMe)](2)center dot 3MeOH center dot H2O (3), trinudear [Ni-3(L-3)(3)]center dot 6H(2)O (4), and a 1-D chain {[Cu2L3(OAc)(2)](2)center dot H2O)(n) (6), of a polydentate, doubly deprotonated, 3,3'-disubstituted bipyridine ligand [L-3](2-) are reported. The X-ray crystal structures demonstrate that the ditopic ligand provides a flexible N-3 donor set for transition metal ions where each binding pocket shifts from fac to intermediate fac/mer to the mer isomer affording a Ni-3 triangle, a Zn-4 tetramer, and a 1-D Cu(II) polymer, respectively. This variation in coordination preference is rationalized with the aim of designing future ligands with controlled coordination modes. Magnetic susceptibility studies on 4 reveal it belongs to the rare family of ferromagnetically coupled [Ni-3] clusters. In contrast, magnetic studies of the 1-D chain 6 reveal weak antiferromagnetic interactions due to the poor orbital overlap of the singly occupied Cu(II) d(x2-y2) orbitals with the one-atom bridge that connects them along the Jahn-Teller distortion axis.