The use of derivatised salicylaldoximes in manganese chemistry has led to the synthesis of a family of approximately fifty hexanuclear ([Mn(III)(6)]) and thirty trinuclear ([Mn(III)(3)]) Single-Molecule Magnets (SMMs). Deliberate, targeted structural distortion of the metallic core afforded family members with increasingly puckered configurations, leading to a switch in the pairwise magnetic exchange from antiferromagnetic to ferromagnetic. Examination of both the structural and magnetic data revealed a semi-quantitative magneto-structural correlation, from which the factors governing the magnetic properties could be extracted and used for predicting the properties of new family members and even more complicated structures containing analogous building blocks. Herein we describe an overview of this extensive body of work and discuss its potential impact on similar systems.