Palladium-catalyzed cycloisomerizations of diarylacetylenes: Synthesis, structures, and physical properties of highly substituted naphthalenes and 8,8 a-dihydrocyclopenta[a]indenes

Depending on the electronic properties of their substituents, the major products generated by palladium-catalyzed cycloisomerizations of diarylalkynes are either highly substituted 8,8a-dihydrocyclopenta[a]indenes 3 or naphthalenes 4. The structures of these compounds were verified by X-ray crystallographic analysis. Many functional groups tolerated the reaction conditions evaluated in this study. The isotope-labeled experiments indicated that added water has a critical role in forming both classes of compounds. The photophysical and electrochemical properties of cycloadducts 3 and their analogues were systematically studied and compared with computational predictions based on density functional theory. Dihydrocyclopenta[a]indenes 3 in either solid or liquid form display strong luminescence, whereas cyclopenta[a]indene 11 j is practically nonfluorescent. The functional groups directly attached to the backbone of compound 3 significantly influenced physical properties. The steric effect arising from the aryl substituents caused different luminescence phenomena, including aggregation-induced and -enhanced emission.