Synthesis of π-Extended Acepleiadylene via Thiophene Fusion on the Seven-Membered Ring

Acepleiadylene (APD), a nonbenzenoid isomer of pyrene with five- and seven-membered rings, exhibits intriguing optoelectronic properties. Herein, we report new π-extension sites on the seven-membered ring of the APD by fusing two thiophene rings. Experimental and theoretical studies reveal that the π-extended derivatives exhibit distinct properties compared with APD and elucidate the impact of the thiophene-fusion mode on the photophysical properties, demonstrating great potential for developing novel APD-based materials with tunable optoelectronic properties.