Supramolecular Assembly and Circularly Polarized Luminescence Regulation of a Chiral Dipyrene-Glutamic Acid Amphiphile

doi:10.6023/cjoc202505001

Abstract

This study focuses on the chiral bipyrene-glutamic acid amphiphilic molecule (PyG), regulating its supramolecular assembly behavior through anti-solvent and host-guest interactions to achieve enhanced circularly polarized luminescence (CPL) and chirality inversion. Our work reveals that in N,N-dimethylformamide (DMF)/H₂O mixed solvents, variations in water content (poor solvent) can modulate the stacking patterns of pyrene chromophores in PyG. At higher water content, pyrene chromophores predominantly exhibit monomer emission, while lower water content favors excimer emission. The distinct overlap modes of pyrene groups significantly influence the chiral optical properties of assemblies, enabling simultaneous inversion of ground-state circular dichroism (CD) and excited-state circularly polarized luminescence (CPL) chiral signals. At water fractions of 40% and 90%, the g_lum values were measured to be －1.31×10^－3 and 1.06×10^－3, respectively. Upon introducing β-cyclodextrin (β-CD) into the system, a 1∶1 complex forms between β-CD and PyG. The molecular chirality of β-CD governs the supramolecular chirality of co-assemblies with both L-PyG/β-CD and D-PyG/β-CD systems displaying negative CPL signals.

Key words: supramolecular chirality, circularly polarized luminescence, self-assembly, chirality inversion, host-guest interactions

Cite this article

Chenyang Zhao, Jingxiao Ren, Guanghui Ouyang, Minghua Liu. Supramolecular Assembly and Circularly Polarized Luminescence Regulation of a Chiral Dipyrene-Glutamic Acid Amphiphile[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4171-4177.

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Fig. & Tab. 4

Figure 1. (a) Molecular structure of L-PyG; (b) UV-vis spectra of L-PyG in different solvents; (c) FL spectra of L-PyG in different solvents (The inserted images are photographs of PyG in different solution, from left to right: 1,4-dioxane, DMF, MeOH); (d) Molecular structure of D-PyG; (e) CD spectra of L-PyG in different solvents; (f) CPL spectra of L-PyG in different solvents For all measurements, the concentration of PyG was 1.3×10－⁴ mol/L, the cuvette path length was 2 mm, excitation wavelengths for fluorescence and CPL spectra were 340 and 320 nm, respectively.

Figure 2. (a) Fluorescence spectra of L-PyG assemblies with fw ranging from 10% to 90%; (b) CD spectra of L-PyG assemblies with fw ranging from 10% to 90%; (c) CD spectra of L-PyG assemblies and D-PyG assemblies at fw=90% and 40%; (d) CPL spectra of L-PyG assemblies with fw ranging from 10% to 90%; (e) SEM image of L-PyG assemblies at fw=40%; (f) SEM image of L-PyG assemblies at fw=90% [PyG]=3.9×10－3 mol/L, cuvette path length 0.1 mm, λex=340 nm and 320 nm for FL and CPL measurements. The blue, red, and black lines represent systems with fw=90%, 40%, and 10%, respectively, while the gray dashed lines correspond to other water fractions.

Figure 3. (a) PXRD patterns of the assemblies at fw=90% (blue line) and fw=40% (red line); (b) FT-IR spectra of the assemblies at fw=90% (blue line) and fw=40% (red line) ([PyG]=3.9×10－3 mol/L in DMF/H2O co-solvents); (c) Schematic ilustration of CPL inversion through water-dependent pyrene stacking

Figure 4. (a) UV-vis spectra of PyG lithium salt with gradually added β-CD (0~4 equiv.) at 298 K ([PyG]=5.23×10⁻⁵ mol/L, cuvette path length=1 cm); (b) Nonlinear fitting curve for a 1∶1 binding model based on the data in Figure 4a; (c) Benesi-Hildebrand plot confirming a 1∶1 binding stoichiometry (binding constant Ka=7.87×103 L•mol－1); (d) Job’s plot for the UV-vis titration of PyG lithium salt with β-CD ([PyG]＋[β-CD]=5.23×10⁻5 mol/L); (e) CPL spectra of L-PyG co-assembled with varying equiv. of β-CD (0, 1, 2, 10 equiv.) (Inset: photographs of samples under 365 nm UV light, from left to right: 0, 1, 2, 10 equiv. β-CD); (f) CPL spectra of D-PyG co-assembled with varying equiv. of β-CD ([PyG]=2.6×10⁻⁴ mol/L, cuvette path length=1 cm)

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