We have structurally and magnetically characterized a total of 12 complexes based on the SingleMolecule Magnet (SMM) [MnIII6O2(sao)(6)(O2CH)(2)(MeOH)(4)] (1) (where sao(2-) is the dianion of salicylaldoxime or 2-hydroxybenzaldeyhyde oxime) that display analogous structural cores but remarkably different magnetic behaviors. Via the use of derivatized oxime ligands and bulky carboxylates we show that it is possible to deliberately increase the value of the spin ground state of the complexes [Mn6O2(Me-sao)(6)(O2CCPh3)(2)(EtOH)(4)](2), [Mn6O2(Et-sao)(6)(O2CCMe3)(2)(EtOH)(5)] (3), [Mn6O2(Et-sao)(6)(O2CPh 2OPh)(2)(EtOH)(4)](4), [Mn6O2(Etsao)(6)(O2CPh (OPh)-O-4)(2)(EtOH)(4)(H2O)(2)](5), [Mn6O2(Me-sao)(6)(O2CPhBr)(2)(EtOH),I (6), [Mn6O2(Et-saO)(6)(O2CPh)(2()EtOH)(4)(H2O)(2)] (7), [Mn6O2(Et-sao)(6)tO(2)CPh(Me)(2)](2)(EtOH)(6)] (8), [Mn6O2(Et-sao)(6)(O2C11H15)(2)(EtOH)(6)] (9), [Mn6O2(Me-saO)(6)(O2C-th)(2)(EtOH)(4)(H2O)2] (10), [Mn6O2(Et-sao)(6)(O2CPhMe)(2)(EtOH)(4)(H2O)(2)] (11), and [Mn6O2(Et-sao)(6)(O2C12H17)(2)(EtOH)(4)(H2O)2] (12) (Et-saoH(2) = 2-hydroxybropiophenone oxime, Me-saoH(2) = 2-hydroxyethanone oxime, HO2CCPh3 = triphenylacetic acid, HO2CCMe3 = pivalic acid, HO2CPh 2OPh = 2-phenoxybenzoic acid, HO2CPh (OPh)-O-4 = 4-phenoxybenzoic acid, HO2CPhBr = 4-bromobenzoic acid, HO2CPh(Me)(2) = 3,5-dimethylbenzoic acid, HO2C11-H-15 = adamantane carboxylic acid, HO2C-th = 3-thiophene carboxylic acid, HO2CPhMe = 4-methylbenzoic acid, and HO2C12H17 = adamantane acetic acid) in a stepwise fashion from S = 4 to S = 12 and, in-so-doing, enhance the energy barrier for magnetization reorientation to record levels. The change from antiferromagnetic to ferromagnetic exchange stems from the "twisting" or "puckering" of the (-Mn-N-O-)(3) ring, as evidenced by the changes in the Mn-N-O-Mn torsion angles.