A set of four [Mn-II((LPy2R)-Py-7)](2+) Complexes, supported by the tetradentate 1,4-bis(2-pyridylmethyl)1,4-diazepane ligand and derivatives with pyridine substituents in the 5 (R = Br) and 6 positions (R = Me and MeO), are reported. X-ray crystal structures of these complexes all show the L(7)py(2)(R) ligands bound to give a trans complex. Treatment of these Mn-II precursors with either H2O2/Et3N or KO2 in MeCN at -40 degrees C results in the formation of peroxomanganese complexes [Mn-III(O-2)(L(7)py(2)(R))](+) differing only in the identity of the pyridine ring substituent. The electronic structures of two of these complexes, [Mn-III(O-2)(L(7)py(2)(H))](+) and [Mn-III(O-2)(L(7)py(2)(Me))](+), were examined in detail using electronic absorption, low-temperature magnetic circular dichroism (MCD) and variable-temperature variable-field (VTVH) MCD spectroscopies to determine ground-state zero-field splitting (ZFS) parameters and electronic transition energies, intensities, and polarizations. DFT and TD-DFT computations were used to validate the structures of [Mn-III(O-2)(L(7)py(2)(H))](+) and [Mn-III(O-2)(L(7)py(2)(Me))](+), further corroborating their assignment as peroxomanganese(III) species. While these complexes exhibit similar ZFS parameters, their low-temperature MCD spectra reveal significant shifts in electronic transition energies that are correlated to differences in Mn-O-2 interactions among these complexes. Taken together, these results indicate that, while the [Mn-III(O-2)(L(7)py(2)(H))](+) complex exhibits symmetric Mn-O-peroxo bond lengths, consistent with a side-on bound peroxo ligand, the peroxo ligand of the [Mn-III(O-2)(L(7)py(2)(Me))](+) complex is bound in a more end-on fashion, with asymmetric Mn-(Operoxo) distances. This difference in binding mode is rationalized in terms of the greater electron-donating abilities of the methyl-appended pyridines and suggests a simple way to modulate MnIII-O2 bonding through ligand perturbations.