An efficient synthetic route to 5,6,11,12-tetrakis(arylethynyl)tetracenes, new Pi-extended rubrene derivs., was developed by [2+4] cycloaddn. of dialkynylnaphthalyne and dialkynylisobenzofuran. Importantly, two alkynyl groups introduced into the aryne exerts a significant effect in lowering the LUMO energy, allowing practical access to sterically overcrowded polycyclic structures through an efficient HOMO-LUMO interaction. Study on the potential reactivity inherent in the peri-ethynyl-substituted tetracenes revealed several interesting reactivities. X-ray anal. of these new マ�-extended derivs. showed distorted structures to reduce steric repulsion due to the existence of the substituents at the peri-positions. [on SciFinder(R)]