This paper deals with syntheses and unequivocal spin identification of prototypical model oligomers for the pi-topological version of an approach to purely organic polyionic polymer ferromagnets, emphasizing that molecular design exploits the topological super pseudo-degeneracy of pi-bonding and pi-antibonding molecular orbitals (pi-HOMOs and pi-LUMOs) appearing close to zero energy in heteroatomic pi-conjugated organic systems, for polycationic and polyanionic organic polymeric high spins, respectively. The oxidation and reduction states of the oligomers designed according to the topological approach are expected to undergo dynamic spin polarization, leading to high-spin ground states for both polycationic and polyanionic model oligomers. One-dimensional and two-dimensional star-burst polycationic model oligomers with heteroatoms participating in pi-conjugation were designed and synthesized Their electronic high-spin ground states have been identified by means of Two-Dimensional Electron Spin Transient Nutation (2D-ESTN) spectroscopy based on an FT pulsed ESR technique to which recently we have exerted ourselves in order to obtain technical advances in molecular spin science underlying the research field of molecule-based magnetics. In this study, the polyketone-based polyanionic high-spin species have been generated also by a dry process, i.e., electron doping by gamma-irradiation in organic glasses.