Three‐Component Synthesis of Dioxaphosphorane‐Fused Diphosphacycles Exhibiting Unique Dynamic Fluorescence “On/Off” Properties

Abstract Rigidly planar polycyclic phosphacycles featuring an internal dioxaphosphorane are promising photofunctional materials. However, the lack of efficient synthetic methods resulted in limited structural diversities which significantly hampered extensive study. Herein, we report a straightforward three‐component synthesis of novel dioxaphosphorane‐fused diphosphacycles with distinctive photophysical properties. Control experiments and theory calculations were performed to account for a plausible reaction mechanism. We also systematically investigated the structure‐property relationships of these unprecedented platforms by combining experiments (X‐ray analysis, optical and redox properties) and theoretical computations. Based on their unique structure and properties, a novel fluorescent switch for pH sensing was revealed by a dynamic ring‐opening/ring‐closing process.