Two new dimeric dysprosium(III) complexes, [Dy(HL)(SCN)]·2CHCN (1) and [Dy(HL)(NO)]·2CHCN·2HO (2), have been assembled using the HL multidentate ligand (HL = 2,2'-((((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))diphenol). The use of different coordination anions for the two complexes results in distinct coordination geometries of the metal sites. The Dy centers in complexes 1 and 2 display capped octahedron and triangular dodecahedron coordination geometries, respectively. Consequently, the two compounds exhibit distinct dc and ac magnetic properties. Complex 1 behaves as a single molecule magnet (SMM) while no SMM behavior is observed for complex 2. Although complexes 1 and 2 possess a similar core of DyO, their different coordination anions lead to two distinct magnetic interactions, namely ferromagnetic and antiferromagnetic, respectively. calculations reveal that these interactions may result from strong intramolecular dipolar couplings that are ferromagnetic for 1 but antiferromagnetic for 2, while exchange couplings are antiferromagnetic in both cases.