Acid/Base and H₂PO₄^– Controllable High-Contrast Optical Molecular Switches with a Novel BODIPY Functionalized [2]Rotaxane

Abstract

A novel multifunctional mechanically interlocked switchable [2]­rotaxane <b>R4</b> containing two molecular stations and rotaxane arms terminated with boron-dipyrromethene (BODIPY) fluorophores and its derivatives were synthesized for the first time by CuAAC click reaction. The shuttling motion of macrocycle between the dibenzylammonium and triazolium recognition sites and the distance dependent photoinduced electron transfer process of <b>R4</b> is demonstrated by utilizing external chemical stimuli (acid/base). Interestingly, the reversible self-assembly process of <b>R4</b> was recognized by the acid–base molecular switch strategy. Notably, two symmetrical triazolium groups acted as molecular stations, H₂PO₄^– receptors, and H-bonded donors. Both [2]­rotaxane <b>R4</b> and thread <b>R2</b> demonstrated excellent optical responses and high selectivity toward H₂PO₄^– ion. The specific motion and guest–host interactions of mechanically interlocked machines (MIMs) were also further explored by quantum mechanical calculations. The thread <b>R2</b> also demonstrated to enable the detection of H₂PO₄^– in RAW 264.7 cells successfully