Preparation of red perylene fluoroionophore containing calix[4]azacrown ether and their ionophoric properties

Novel new red-light emitting perylene fluoroionophore N,N'-dipropyl-1,7- bis(calix[4]azacrown-5-crown-5)-3,4,9,10-perylene tetracarboxy diimide (3) was prepared by reacting N,N′-dipropyl-1,7-dibromo-3,4,9,10-perylene tetracarboxy diimide (1) with calix[4]azacrown-5-crown-5. Also the alternating copolymer (4) with similar repeating unit was prepared reacting by calix[4]bisazacrown-5 with 1. Metal ion binding by 3 and 4 leads to a blue-shift of absorption band and emission spectra. When ionophoric characteristics were investigated by binding alkali, alkali earth metal and various metal ions, polymeric ionophores displayed large fluorescence decreasing effects with K ⁺, Ag⁺ and Ba²⁺, which was rationalized by photo-induced charge transfer (PCT).