Switchable Circularly Polarized Luminescence in Supramolecular Gels through Photomodulated FRET

While the tremendous deal of efforts has been dedicated to the design and fabrication of materials with circularly polarized luminescence (CPL), the development of the chiroptical switch between different CPL signals is one of the important routes toward its application. Here, we prepared a supramolecular gel from the coassemblies containing a chiral gelator (9-fluoren-methoxycarbonyl-functionalized glutamate derivatives, FLG), a fluorescent molecule [(rhodamine B, RhB) or (2',7'-dichlorofluorescein sodium salt, DCF)], and a photochromic molecule [1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, DAE], thus constructing photomodulated switchable CPL soft materials. It was found that FLG could form supramolecular gel in ethanol and self-assemble into left-handed twisted nanostructures. During the formation of a co-gel with RhB (or DCF) and DAE, the chirality of FLG could be effectively transferred to both the fluorescent and photochromic components, which induced them with chiroptical properties including CPL and circular dichroism (CD). DAE undergoes a reversible transition between the achromatous open state and the dark purple closed state in the co-gel under alternating irradiation with UV and visible light. During such a process, an intermolecular Förster resonance energy transfer (FRET) behavior from fluorescent RhB to ring-closed DAE caused the emission quenching of RhB, which led to CPL silence of RhB in the co-gel. Subsequent irradiation with visible light caused the restoration of the emission and CPL activity with the restored open state. These changes could be repeated many times upon alternate UV and visible irradiation. Therefore, a reversible CPL switch was fabricated in supramolecular gels through the photomodulated FRET process.