The preparation and detailed characterizations of the high-spin seven-coordinate complexes [M(kappa N-7-L)](ClO4)(2) (M = Mn (II), Fe(II); L = N,N,N',N=tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine) are described. The X-ray crystal structures reveal seven-coordinate metal complex ions. Consideration of continuous shape measures reveals that the coordination environments about the metal ions are better described as having (C-s) face-capped trigonal prismatic symmetry than (C-2) pentagonal bipyramidal symmetry. The (S=5/2) Mn(II) species shows complicated X-band electron paramagnetic resonance (EPR) spectra and broad unrevealing H-1 NMR spectra. In contrast, the (S=2) Fe(II) complex is EPR-silent and shows completely interpretable H-1 NMR spectra containing the requisite number of paramagnetically shifted peaks in the range delta +150 to -60. The C-13 NMR spectra are likewise informative. Variable-temperature H-1 NMR spectra show coalescences and decoalescences indicative of an intramolecular process that pairwise-exchanges the nonequivalent pyridylmethyl "arms" of the two bis(pyridylmethyl)amine (bpa) domains. A suite of NMR techniques, including T-1 relaxation measurements and variable-temperature H-1-H-1 correlation spectroscopy, H-1-H-1 total correlation spectroscopy, H-1-H-1 nuclear Overhauser effect spectroscopy/exchange spectroscopy, and H-1 - C-13 heteronuclear multiple-quantum coherence experiments, has been used to assign the NMR spectra and characterize the exchange process. Analysis of the data from these experiments yields the following thermodynamic parameters for the exchange: Delta H-double dagger = 53.6 +/- 2.8 kJ mol(-1), Delta S-double dagger = -10.0 +/- 9.8 J K-1 mol(-1), and AGE (298 K) = 50.6 kJ mol(-1). Density functional theory (B3LYP) calculations have been used to explore the energetics of possible mechanistic pathways for the underlying fluxional process. The most plausible mechanism found involves dissociation of a pyridylmethyl arm to afford a strained six-coordinate species followed by rebinding of the arm in a different position to afford a new seven-coordinate transition state in which the pyridylmethyl arms within each bpa domain are essentially equivalent; the calculated energy barrier for this process is 53.5 kJ mol(-1), in good agreement with the observations.