Citation: Wang Hanxiao, Xu Lifei, Liu Minghua. Supramolecular Gel Based on Amphiphilic Quinoxaline: Chirality Inversion and Chiroptical Switch with Multiple Stimuli-Responsiveness[J]. Acta Physico-Chimica Sinica, ;2020, 36(10): 191003. doi: 10.3866/PKU.WHXB201910036 shu

Supramolecular Gel Based on Amphiphilic Quinoxaline: Chirality Inversion and Chiroptical Switch with Multiple Stimuli-Responsiveness

Wang Hanxiao ¹ ,
Xu Lifei ^1,2 ,
Liu Minghua ^1,2,,

1.
Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
2.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Corresponding author: Liu Minghua, liumh@iccas.ac.cn
Received Date: 17 October 2019
Revised Date: 18 November 2019
Accepted Date: 20 November 2019
Available Online: 27 November 2019
Fund Project: China Postdoctoral Science Foundation 2017M620915the National Natural Science Foundation of China 21890734The project was supported by the National Natural Science Foundation of China (21890734) and China Postdoctoral Science Foundation (2017M620915)

The regulation of supramolecular chirality has applications in various aspects including asymmetric catalysis, chiral sensing, optical materials and smart devices. Additionally, it provides opportunities for the simulation of important activities in living organisms and the clarification of their mechanisms. Herein, we synthesized a chiral gelator SQLG (styrylquinoxalinyl L-amino glutamic diamide) containing a π-conjugated headgroup by introducing the quinoxaline-derived moiety into L-glutamic diamide-based amphiphile via two simple condensation steps. SQLG self-assembled into nanofibers through multiple intermolecular interactions, including π–π stacking, hydrogen bonding and van der Waals interaction, leading to gelation of various organic solvents ranging from nonpolar to polar ones. Chirality transfer from the chiral center to the supramolecular level was observed when organogels formed, which manifested itself in circular dichroism (CD) spectra. The organogels formed in polar solvents such as N, N-dimethylformamide (DMF) and nonpolar solvents such as toluene exhibited opposite signals of supramolecular chirality, attributed to different hydrogen bonding strengths and thus two different types of gelator stacking modes of the gelators which was confirmed by infrared spectroscopy (IR) and X-ray diffraction (XRD). Circular polarized luminescence (CPL) denotes left-handed or right-handed circularly polarized light with different intensities emitted by the chiral luminescent system, and it characterizes the chirality of the excited state, which finds potential application in fields such as 3D optical displays, optical data storage, polarization-based information encryption and bioencoding. Owing to the strong fluorescence and supramolecular chirality, the toluene gel emitted right-handed circular polarized luminescence upon excitation, while the gel formed in DMF did not exhibit CPL emission because of its relatively weak fluorescence. Furthermore, the organogels responded rapidly and distinctly to the stimulus of acid due to the proton-accepting sites in the quinoxaline skeleton. Utilizing NMR spectroscopy, we found that the two nitrogen atoms in the quinoxaline moiety could be protonated upon acidification. During the process, intramolecular charge transfer (ICT) was significantly strengthened and the driving forces of self-assembly underwent remarkable changes, resulting in the collapse of the yellow transparent organogel into a red dispersion. Meanwhile, transformation from nanofibers to nanospheres was observed using a scanning electron microscope (SEM). With change in stacking modes in the supramolecular assembly, a complete inversion of the CD signal was detected. The CPL signal was found to be switched off, which along with the other changes of the system could subsequently be recovered by neutralization of the entire system. Therefore, we constructed a chiroptical switch with multiple stimuli-responsiveness through the introduction of an acid-sensitive π-conjugated moiety into the L-glutamic diamide-based chiral amphiphile.
- Chiroptical switch,
- Gel,
- Multi-responsiveness,
- Quinoxaline derivative,
- Supramolecular chirality
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