Metal–organic materials (MOMs) represent an emerging class of materials that have attracted the imagination due to highly functional character and significant contributions in numerous applications areas including, but not limited to, catalysis, sensors, separations, transport of hydrogen, and drug delivery. MOMs are comprised of metal moieties and organic ligands and are exemplified by a diverse group of discrete (e.g. metal–organic clusters) or polymeric structures (e.g. coordination polymers or metal–organic frameworks (MOFs)). Polymeric MOMs demonstrate how crystal engineering holds great promise for control of the arrangement of atoms in space due largely to the ability to target specific molecular building block (MBB) with given geometry and directionality prior to the assembly process as well their inherent modularity and prototypal for a diverse range of structures. Recently more attention has been paid to the multinuclear metal-clusters as supermolecular building blocks (SBBs), which can be used as nodes with enhanced variety of coordination algorithms and size compare with a single metal ion and give rise to a family of cluster-based polymers. Apart from design perspective, multinuclear clusters may introduce their inherent extraordinary physical properties to the polymeric structure. The cluster-based polymers may be assembled from pre-designed and pre-synthesized SBBs. In our report we will demonstrate how the tri-, tetra-, and hexanuclear metal carboxylate clusters which possess multiple metal-oxygen coordination bonds that result in the generation of rigid nodes with fixed geometry that, when combined with organic ligands of specific geometry, lead to the construction of desired polymeric MOMs. The linear trinuclear [MnII 3(O2CCHMe2)6] and tetranuclear [MnII 2MnIII 2O2(O2CCMe3)6], [Fe4O2(O2CCMe3)8] clusters of different connectivity having {Me4(μ3-O)2} cores (Me=Mn, Fe) have been used for design and synthesis of 1D coordination polymers in which cluster moieties are connected by polypyridyl or hexamethylentetramine (hmta) linkers. The most versatile polymeric architecture has been achieved with μ3-oxo trinuclear homo- {Fe3(μ3-O)} and {MnFe2(μ3-O)} heterometalic type clusters. In combination with bipyridyl or hmta linkers the different 1D chains, 2D sheets polymers as well as a 3D highly porous MOF (Fig.1) with a large total potential solvent area of 44.1% per unit cell volume have been obtained and structurally characterized. The 1D polymers have been also constructed from nanoscale hexanuclear manganese carboxylate clusters featuring the {MnII 4MnIII 2(μ4-O)2} core of composition [Mn6O2(O2CCMe3)10] with pyrazine, nicotinamide, or 1,2-bis(4-pyridyl)ethane spacer ligands, while using isonicotinamide as linker results in 2D porous polymer.figureFig.1. Individual 3D 3-connected bimodal uniform (83)c (etc) net (a) based on oxotrinuclear cluster building block and 4,4’-bipyridine exo-ligands and porous MOF channel crystal structure (b) resulted from six-fold interpenetration of such nets.