Fabrication of Helical Nanoribbon Polydiacetylene via Supramolecular Gelation: Circularly Polarized Luminescence and Novel Diagnostic Chiroptical Signals for Sensing.

Abstract

Four kinds of commercially available diacetylene (DA) monomers with different chain length, diacetylene positions were fabricated into the organogels via mixing with a chaperone gelator, an amphiphilic l-histidine ester derivative LHC18 that can help the nongelator to form gels. Upon photo irradiation with a 254 nm UV light, the white gels underwent topochemical reaction and turned into red or blue gels, depending on the DA monomer structures. Through the gel formation, the molecular chirality of LHC18 can be transferred to the polydiacetylene (PDA) and helical nanoribbon structures were obtained. The blue gels showed a clear response to stimuli such as pH variation, heating, mechanical force and organic solvents, and turned into red gels. Interestingly, the blue gel showed strong supramolecular chirality, which could be turned off or changed into red phase CD signals. Such changes in chiroptical signals depended on the external heating and various organic solvents. In the case of heating, the blue gel changed into red one, which showed both strong CD signals and circularly polarized luminescence. In the case of organic solvents, although all the tested solvents made the blue gel to red, only some of them could keep the CD signals, thus providing additional sensing capacity of the PDA system. So far, the blue-to-red color change and the "fluorescence on" was widely used as colorimetric and fluorogenic diagnostic signals for PDA, here we showed an additional chiroptical diagnostic signal for a more precise sensing by using the helical PDA.