Controlled organization of high-spin complexes and single-molecule magnets is a great challenge in molecular magnetism in order to study the effect of the intercomplex magnetic interactions on the intrinsic properties of a given magnetic object. In this work, a new S-T = 7 trinuclear mixed-valence Mn complex, [Mn(III)Mn(II)2(L-A)(2)(Br)(4)(CH3OH)(6)] Br(CH3OH)(15)center dot(H2O)(0.5) (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H2LABr = 1-(3-bromo2,2-bis-(hydroxymethyl)propyl)pyridinium bromide). Using azido anions as bridging ligands and different pyridinium-functionalized 1,3-propanediol ligands (H2LBBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-4-picolinium bromide; H2LCBr = 1-(3-bromo-2,2-bis(hydroxymethyl)propyl)-3,5-lutidinium bromide), the linear [Mn(III)M(2)(II)L(2)x(4)](+) building block has been assembled into one-dimensional coordination networks: [(MnMn2II)-Mn-III(L-A)(2)(Br)(4)(CH3OH)(4)(N-3)]center dot((C2H5)(2)O)(1.25) (2 infinity), [(MnM2II)-M-III(L-B)(2)(Br)(4)(C2H5OH)(CH3OH)(H2O)(2)(N-3)]center dot(H2O)(0.25) (3 infinity), and [(MnMn2II)-Mn-III(L-C)(2)(Cl)(3.8)(Br)(0.2)(C2H5OH)(3)(CH3OH)(N-3)] (4 infinity). The syntheses, characterization, crystal structures, and magnetic properties of these new [Mn-3]-based materials are reported.