The controlled organization of high-spin complexes, eventually single-molecule magnets, is a great challenge in molecular sciences to probe the possibility to design sophisticated magnetic systems to address a large quantity of magnetic information. The coordination chemistry is a tool of choice to make such materials. In this work, high-spin S-T = 22 [Mn-10] complexes, such as [(Mn6Mn4II)-Mn-III(L-1)(6)(mu(4)-O)(4)(mu(3)-N-3)(4)(CH3CN)(11)-(H2O)]ce nter dot(ClO4)(2)center dot(CH3CN)(8.5) (1), have been assembled using (i) 1,3-propanediol derivatives as chelating ligands to form the [Mn-10] core units and (ii) dicyanamide or azide anions as linkers to synthesize the first 2D and 3D [Mn-10] -based networks: [Mn-6(III)-Mn-4(II)(L-2)(6)(mu(3)-N-3)(4)(mu(4)-O)(4)(CH3OH)(4)(dca)(2)] (2) and [(Mn6Mn4II)-Mn-III(L-3)(6)(mu(3)-N-3)(4)(mu(4)-O)(4)(N-3)(2)]center dot(CH3OH)4 (3). The synthesis of these compounds is reported together with their single-crystal X-ray structures and magnetic properties supported by DFT calculations. In the reported synthetic conditions, the stability of the [Mn-10] complex is remarkably good that allows us to imagine many new materials combining these high-spin moieties and other diamagnetic but also paramagnetic linkers to design for example ordered magnets.