The synthesis of new silylethyne-substituted hexacene derivatives to investigate their solubility, stability, and pi-stacking is reported. It was found that "butterfly" dimerization, rather than photooxidation, is the dominant decomposition pathway for these molecules and that stability can be enhanced by functionalization to prevent close contact between specific regions of the aromatic core. Dimerization regioselectivity can be altered by suitable engineering of the solid-state arrangement of the chromophores.