Trianionic spin-quartet and tetraanionic spin-quintet molecular clusters derived from m-dibenzoylbenzene in solution were identified by CW-ESR/pulse-ESR based two-dimensional electron spin transient nutation spectroscopy, and their spin and clustering structures in the ground state were determined in terms of a D-tensor based phenomenological approach and DFT calculations. The molecular structures obtained semiempirically are supported by DFT-based quantum chemical calculations. The DFT calculations have been tested for a sodium ion bridged fluorenone-based cluster, [fluorenone⁻˙ {Na⁺(dme)₂}]₂, whose crystal structure was reported in the literature [H. Bock, H.-F. Herrmann, D. Fenske and H. Goesmann, Angew. Chem., Int. Ed. Engl., 1988, 27, 1067], reproducing the experimentally determined moelcular structure of the dimer cluster. It is suggested that both the quartet and quintet clusters in the 2-MTHF glass and solution form the cross-typed structures with the two m-dibenzoylbenzene moieties in cis-configuration. A dianionic spin-triplet m-dibenzoylbenzene derivative was detected for the first time and its charge and spin densities were studied by the quantum chemical calculations. The high-spin states of the open-shell entities under study were confirmed by X-band pulse-ESR based electron spin nutation spectroscopy in organic frozen glasses. The D values and other spin Hamiltonian parameters of all the polyanionic high-spin species were determined by the hybrid eigenfield spectral simulation for fine-structure ESR spectra. m-Dibenzoylbenzene provides pseudo-degenerate π-LUMOs arising from its topological symmetry of the π-electron network and its dianion in the triplet ground state is a prototypical model for topologically-controlled genuinely organic ferromagnetic metals.