The one-flask synthesis of seven-membered free-base BOPYINs (NBs) using benzo indole and β-substituted pyrrole moieties has been reported. This stable cis-configuration of diarylethenes with Aggregation Induced Emission (AIE) properties was locked by the seven-membered ring hydrogen bond (HB) and steric hindrance, which made ‘Excited-State Intramolecular Proton Transfer (ESIPT)’ phenomena take place in this benchmark.