Having established that molecules with general formulae [MnIII6O2(R-sao)6(O2CR)2(L)4–6] ([Mn6]) and [MnIII3O(R-sao)3(X)(L)3] ([Mn3]) (saoH2 = salicylaldoxime; R = H, Me, Et etc; X = RCO2−, ClO4−; L = solvent), with the latter being the analogous “half” molecules of the former, exhibit the phenomenon of single-molecule magnetism, we have exploited them as building blocks to construct supramolecular architectures by means of host–guest interactions and coordination driven self-assembly. A number of discrete and infinite architectures, namely [MnIII3O(Ph-sao)3(4Cl-sbz)3(MeOH)3]2(OH)(ClO4)·2MeOH (1·2MeOH), [MnIII3O(Ph-sao)3(4Me-sbz)3(EtOH)3]2(OH)(NO3) (2), {[MnIII3O(Et-sao)3(4,4′-bpy)2(MeOH)] ClO4·1.5MeOH·Et2O}n (3·1.5MeOH·Et2O), {[MnIII3O(sao)3(4,4′-bpe)1.5]ClO4·3MeOH}n (4·3MeOH) and [{MnIII3O(Et-sao)3(O2CPh)(EtOH)}2{4,4′-bpe}2] (5), based on the molecular triangle [Mn3] and various pyridyl-type ligands (4Cl-sbz = 4-chlorostilbazole, 4Me-sbz = 4-methylstilbazole, 4,4′-bpy = 4,4′-bipyridine and 4,4′-bpe = trans-1,2-bis(4-pyridyl)ethylene) were obtained and structurally and magnetically characterized.