  This article takes a broad view of the understanding of magnetic bistability
and magnetic quantum tunneling in single-molecule magnets (SMMs), focusing on
three families of relatively simple, low-nuclearity transition metal clusters:
spin S = 4 Ni4, Mn(III)3 (S = 2 and 6) and Mn(III)6 (S = 4 and 12). The Mn(III)
complexes are related by the fact that they contain triangular Mn3 units in
which the exchange may be switched from antiferromagnetic to ferromagnetic
without significantly altering the coordination around the Mn(III) centers,
thereby leaving the single-ion physics more-or-less unaltered. This allows for
a detailed and systematic study of the way in which the individual-ion
anisotropies project onto the molecular spin ground state in otherwise
identical low- and high-spin molecules, thus providing unique insights into the
key factors that control the quantum dynamics of SMMs, namely: (i) the height
of the kinetic barrier to magnetization relaxation; and (ii) the transverse
interactions that cause tunneling through this barrier. Numerical calculations
are supported by an unprecedented experimental data set (17 different
compounds), including very detailed spectroscopic information obtained from
high-frequency electron paramagnetic resonance and low-temperature hysteresis
measurements. Diagonalization of the multi-spin Hamiltonian matrix is necessary
in order to fully capture the interplay between exchange and local anisotropy,
and the resultant spin-state mixing which ultimately gives rise to the
tunneling matrix elements in the high symmetry SMMs (ferromagnetic Mn3 and
Ni4). The simplicity (low-nuclearity, high-symmetry, weak disorder, etc..) of
the molecules highlighted in this study proves to be of crucial importance.
