The exceptionally strong acceptor ability of benzonitronyl nitroxides (~0 V vs SCE), D-A-D (S =½) triads were designed in order to investigate the effect of spin state on charge transport in organic semiconductors. Two classes of triads were investigated; antiferromagnetic (1) and ferromagnetic (2) semiconductors, in which the conductivity was found to be ~10-4 to 10-6 S cm-1 (300 K). Structural characterization of the triads in the solid state by XRD reveal slipped π stacks arising from π-π and intermolecular D-A interactions, providing pathways for magnetic exchange and charge transport. An inspection of the crystallographic packing, combined with ab initio methodologies allows a computational evaluation of all magnetic pathways in a crystal to obtain the network of JAB interactions (i.e. magnetic topology), which gives rise to the overall bulk magnetism of the solid once it is expanded along the three crystalline directions of the crystal. For radical 1, DFT calculations predict antiferromagnetic interactions, on the order of J = −3.4 cm-1, suggesting that π−π interactions provide the dominant exchange pathway giving rise to a low spin ground state. For radical 2, the D-A π-dimer was predicted computationally to possess a high spin ground state with a strength of J = +27.0 cm-1. The increased slippage in the π-dimer with respect to 2 results in a decreased overlap between magnetic orbitals, which can be associated with an enhanced FM behavior in the magnetic exchange pathway. We have computed the Density Of States (DOS) and band structure for 1 and 2 on their RT X-ray recorded structures and crystalline unit cells, obtaining band gaps that account for 0.55 eV and 0.73 eV, respectively. Overall, our results support that the D/A stacking pattern in radical 2 offers improved conducting properties over the π-π contacts as in compound 1, both of them lying in the semiconducting regime. The lower conductivity of 1 is associated with trapping associated with antiferromagnetic spin-spin interactions, consistent with a spin barrier to charge transport.