Abstract: | Oxidative photocyclization of 4‐(2‐arylvinyl)benzoa]quinolizinium salts ( 6 ) gave five‐ or six‐mem‐bered rings depending on the aryl substituent. The olefins 6a and 6b with a phenyl or naphthyl substituent resulted in a normal six‐membered ring formation to afford 6a‐azoniapicene and 6a‐azoniabenzob]picene salts ( 7 and 8 ), respectively. In contrast, the photo‐reaction of pyridyl substituted derivative 6c resulted in novel five‐membered ring formation to yield 3b‐azonia‐5‐(2‐pyridyl)acephenanthrylene salt ( 10 ). |