The synthesis and characterization of three Dy-2 compounds, [Dy-2(HL1)(2)(NO3)(4)] (1), [Dy-2(L-2)(2)(NO3)(4)] (2), and [Dy-2(HL3)(2)(NO3)(4)] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl and alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), and 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. The compounds are rare examples of alkoxide-bridged {Dy-2} complexes and display capped square antiprism coordination geometry around each Dy-III ion. Changes in the ligand field environment around the Dy-III ions brought about through variations in the ligand donors can be gauged from the magnetic properties, with compounds 1 and 2 showing antiparallel coupling between the Dy-III ions and 3 showing parallel coupling. Furthermore, slow relaxation of the magnetization typical of SMM behavior could be observed for compounds 2 and 3, suggesting that small variations in the ligand field can have a significant influence on the slow relaxation processes responsible for SMM behavior of Dy-III-based systems.