Highly Efficient Förster Resonance Energy Transfer Modulations of Dual-AIEgens between a Tetraphenylethylene Donor and a Merocyanine Acceptor in Photo-Switchable [2]Rotaxanes and Reversible Photo-Patterning Applications

Abstract

A series of novel photo-switchable [2]rotaxanes (i.e., <b>Rot-A-SP</b> and <b>Rot-B-SP</b> before and after shuttling controlled by acid-base, respectively) containing one spiropyran (SP) unit (as a photochromic stopper) on the axle and two tetraphenylethylene (TPE) units on the macrocycle were synthesized via click reaction. Upon UV/visible light exposure, both mono-fluorophoric rotaxanes <b>Rot-A-SP</b> and <b>Rot-B-SP</b> with the closed form (i.e., non-emissive SP unit) could be transformed into the open form (i.e., red-emissive merocyanine (MC) unit) to acquire their respective bi-fluorophoric <b>Rot-A-MC</b> and <b>Rot-B-MC</b> reversibly. The aggregation-induced emission (AIE) properties of bi-fluorophoric TPE combined with MC AIEgens of these designed rotaxanes and mixtures in semi-aqueous solutions induced interesting ratiometric photoluminescence (PL) and Förster resonance energy transfer (FRET) behaviors, which were further investigated and verified by dynamic light scattering (DLS), X-ray diffraction (XRD), and time-resolved photoluminescence (TRPL) measurements along with theoretical studies. Accordingly, in contrast to the model axle (<b>Axle-MC</b>) and the analogous mixture (<b>Mixture-MC</b>, containing the axle and macrocycle components in a 1:1 molar ratio), more efficient FRET behaviors and stronger red PL emissions were obtained from dual-AIEgens between a blue-emissive TPE donor (PL emission at 468 nm) and a red-emissive MC acceptor (PL emission at 668 nm) in both novel photo-switchable [2]rotaxanes <b>Rot-A-MC</b> and <b>Rot-B-MC</b> under various external modulations, including water content, UV/Vis irradiation, pH value, and temperature. Furthermore, the reversible fluorescent photo-patterning applications of <b>Rot-A-SP</b> in a powder form and a solid film with excellent photochromic and fluorescent behaviors are first investigated in this report.