A detailed study of the electronic structure of seven-coordinate Mn(II), Co(II), and Ni(II) complexes with the lariat ether N,N'-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 (U) is presented. These complexes represent new examples of structurally characterized seven-coordinate (pentagonal bipyramidal) complexes for the Mn(II), Co(II), and Ni(II) ions. The X-ray crystal structures of the Mn(II) and Co(II) complexes show C-2 symmetries for the [M(L-1)](2+) cations, whereas the structures of the Ni(II) complexes show a more distorted coordination environment. The magnetic properties of the Mn(11) complex display a characteristic Curie law, whereas those of the Co(II) and Ni(II) ions show the occurrence of zero-field splitting of the S = 3/2 and 1 ground states, respectively. Geometry optimizations of the [M(L-1)](2+) systems (M = Mn, Co, or Ni) at the DFT (B3LYP) level of theory provide theoretical structures in good agreement with the experimental data. Electronic structure calculations predict a similar ordering of the metal-based beta spin frontier MO for the Mn(II) and Co(II) complexes. This particular ordering of the frontier MO leads to a pseudodegenerate ground state for the d(8) Ni(II) ion. The distortion of the C-2 symmetry in [Ni(L-1)](2+) is consistent with a Jahn-Teller effect that removes this pseucloclegen e racy. Our electronic structure calculations predict that the binding strength of L-1 should follow the trend Co(II) approximate to Mn(II) > Ni(II), in agreement with experimental data obtained from spectrophotometric titrations.