Thiopyran-Fused Polycyclic Aromatic Compounds Synthesized via Pt(II)-Catalyzed One-Pot Ring-Expansion and 6-endo Cyclization Reactions

Abstract

A series of thiopyran-fused polycyclic aromatic hydrocarbons (PAHs) have been straightforwardly synthesized from 2,5-di(1-en-3-ynyl)thiophene-containing precursors via onepot ring-expansion and 6-endo cyclization reactions. The reaction monitoring and the density function theoretical calculation suggest that the ring-expansion reaction occurs prior to 6-endo cyclization. Moreover, the absorption profiles of the thiopyran-fused PAHs suggest that the π-conjugation extension on the side of the cyclopentadiene ring in the cyclopenta[b]thiochromene core is predominant in prolonging the effective conjugation length, while the effect from extension on the other side is negligible. Furthermore, all of the thiopyran-fused PAHs exhibit halochromic properties. Upon the addition of trifluoromethanesulfonic acid, fluorescence "off−on" switches can be found for these thiopyran-fused PAHs. Therefore, this work not only provides a new synthetic approach for one-pot ring-expansion and 6-endo cyclization reactions but also expands the diversity of thiopyran-fused PAHs.