The recent accomplishments in obtaining strong ferromagnetic exchange interactions in organic diradicals have made the field quite fascinating and even more promising toward its technological applications. In this context, herein, we report a unique combination of remarkably strong ferromagnetic exchange interactions coupled with molecular rigidity, utilizing superstable Blatter’s radical as a spin source. The planar analogues of the parent Blatter’s radical obtained by annulation with a chalcogen coupled to nitronyl nitroxide (NN) are investigated using density functional theory along with the wave function-based multiconfigurational self-consistent field methods, for example, complete active space self-consistent field (CASSCF)–N-electron valence state perturbation theory (NEVPT2). The calculations reveal phenomenal modulation in exchange couplings upon annulation such that remarkably strong ferromagnetic interactions are realized especially for a certain class of the Blatter-NN diradicals. The modulation of spin–spin interactions is rationalized by variation in spin density distribution and molecular torsional angles. We demonstrate that annulation in OMMs opens an additional coupling pathway via auxiliary X-atom acting as the atomic relay center which strongly manipulates the magnitude of exchange couplings.