Ab initio calculations on pyridine and pyridinium analogues of m-xylylene indicate that the neutral heterocycle is essentially equivalent to benzene as a ferromagnetic coupling unit, while the cationic pyridiniums behave much differently. Depending on the substitution pattern, a protonated pyridine can serve as a ferromagnetic coupling unit or an antiferromagnetic coupling unit. Both valence bond and molecular orbital arguments provide qualitative rationalizations of these results, In an effort to test the theoretical predictions, bis(trimethylenemethane) analogues of the pyridine and pyridinium biradicals were synthesized and analyzed by electron paramagnetic resonance spectroscopy. General support for the theoretical predictions is obtained.