Abstract
Metamaterials with supramolecular chirality have been widely developed in many fields, and their assembly modes provide valuable insights for understanding living systems. In this work, we achieved for the first time the inversion of supramolecular chirality in organogels using a low-polarity achiral solvent. Furthermore, the regulation of supramolecular chirality was achieved through structural modification of the achiral moieties. Additionally, the impact of hydrogen bond variability on the modulation of supramolecular chirality was investigated by replacing the O atom with the N atom. Subsequently, the mechanisms governing supramolecular chirality modulation through low-polarity solvents and weakly polar structural motifs was elucidated. The results demonstrate that weak-polarity solvents, achiral long-chain moieties, and hydrogen bonds can individually serve as effective modulators for regulating intermolecular assembly patterns, thereby exerting critical influence on the emergence of supramolecular chirality. These findings establish a robust foundation for the precise construction and manipulation of supramolecular chirality in organogel systems.
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Introduction
Supramolecular chiral organogels have garnered increasing attention due to their potential applications in chiroptical switching1,2,3,4,5,6, sensor devices2,4,5,7,8, and circularly polarized luminescence9,10. To enhance their practical applicability, effective regulation of supramolecular chirality in organogels becomes imperative1,11,12,13,14,15,16,17,18,19,20,21,22. Current strategies for chirality modulation in organogel systems are primarily categorized into two approaches: chiral factor-based regulation and achiral factor-mediated regulation23. The chiral factor-based approach predominantly relies on modifying the intrinsic molecular chirality of gelators to manipulate supramolecular chirality24,25,26,27,28,29,30, typically governed by the majority rule31,32,33,34,35 and sergeant-and-soldiers rule32,36,37,38,39. Although extensively investigated in supramolecular chirality research, however, this strategy requires either altering the intrinsic chiral configuration of gelators or introducing additional chiral moieties, which has dramatically complicated the flexible chirality modulation. In contrast, achiral factor-mediated regulation circumvents the need for modifying molecular chiral configuration, transcending the conventional limitations of chiral factor-based regulation and offering more flexible, cost-effective, and efficient strategies4,40,41,42. Consequently, achiral factor-driven modulation of supramolecular chirality in organogels has recently emerged as a burgeoning research frontier43,44,45.
Recent advancements have witnessed growing reports on achiral factor-mediated regulation of supramolecular chirality in gel systems. Notably, the Liu group pioneered chiral modulation through structural modification of gelator side chains46. Zhao and co-workers achieved supramolecular chirality inversion via coordination with transition metal ions47,48. Subsequent investigations by Liu et al. revealed time-dependent chirality switching in gel systems49. More systematic studies have demonstrated chirality manipulation through variations in achiral segments within gelator design, collectively establishing fundamental mechanisms for supramolecular chirality control3,50,51. Current research in this field predominantly focuses on solvent polarity effects for chirality regulation. However, the potential of weak polarity solvent engineering in manipulating supramolecular gel chirality remains largely unexplored52,53, presenting a critical knowledge gap in achiral modulation strategies.
In this work, a series of phenylalanine-derived organogelators (L-PheOn) capable of supramolecular chirality inversion in low-polarity achiral solvents. A systematic approach was implemented to explore chirality modulation mechanisms (Fig. 1). Initially, a simple solvent shift from weakly polar solvents, such as n-octane to cyclohexane, successfully inverted supramolecular chirality without structural modification of gelators. Subsequently, the modulation of supramolecular chirality was similarly achieved by modification of the achiral tail chain of L-PheOn(Fig. 1a). To elucidate hydrogen bonds effects on chiral expression, amide-functionalized analogs (L-PheNn) were synthesized by replacing ester linkages with stronger hydrogen bonds moieties. Enhanced intermolecular hydrogen bonds within gel assemblies were found to suppress chirality inversion (Fig. 1b). The above results demonstrate that all these achiral factors play a crucial role in the regulation of supramolecular chirality. Finally, to elucidate the assembly mode of this supramolecular gel, we conducted computational simulations on the supramolecular organogel system. Our findings demonstrate that the solvent environment, the length of the hydrophobic end chains, and hydrogen bond interactions critically govern the self-assembly behavior of the aggregates. These insights provide a foundation for the effective modulation of supramolecular gel chirality through achiral factors.
a Supramolecular chiral inversion of L-PheOn in low-polarity achiral solvent solvents, b Supramolecular chirality modulation of L-PheNn in low-polarity achiral solvent solvents.
Results and discussion
Effect of low-polarity achiral solvents on supramolecular chirality
Supramolecular chirality of L-PheO6 gels in two weakly polar solvents was initially characterized by SEM. In n-octane, P-helical chirality was shown (Fig. 2a), while in cyclohexane, M-helical chirality was shown (Fig. 2b). To elucidate the origin of this solvent-dependent chiral inversion, XRD analysis was employed to determine the possible structural arrangement of the organogel formed. The XRD profile of the cyclohexane gel of L-PheO6 exhibited two broad peaks at 19.21° and 23.73° (Fig. 2e), which suggests that the form of assembly of L-PheO6 in cyclohexane mainly relies on hydrogen bonds54 and π-π stacking45,55,56. In contrast, the XRD spectrum of the L-PheO6 in n-octane gel showed only hydrogen bonds (19.38°), and no π-π stacking interaction was clearly observed. This phenomenon may be attributed to the spatial structure effect of the n-octane solvent on the gel system. Specifically, the n-octane solvent likely hindered the formation of sufficient π-π stacking interactions within the L-PheO6 gel aggregates, leading to an assembly pattern distinct from that observed in the L-PheO6 cyclohexane gel and ultimately reversing the supramolecular chirality compared to the cyclohexane system.
a SEM of L-PheO6 in n-octane, b L-PheO6 in cyclohexane, c L-PheN6 in n-octane, d L-PheN6 in cyclohexane, e XRD spectra of organogel, f FTIR spectra of organogel, g Geometric lengths of organogelators, which were obtained from the geometric conformation of the dimer with the lowest energy.
To probe structural determinants of chiral modulation, an amide-functionalized analog (L-PheN6, Fig. 2g) was synthesized. These analog features dual hydrogen bonds-capable amide moieties instead of ester groups in L-PheO6, whereas the ester group in L-PheO6 was not able to generate additional hydrogen bonds (Fig. 2g). SEM results showed that both cyclohexane gels and octane gels of L-PheN6 exhibited the same P-helical chirality (Fig. 2c, d). XRD spectra revealed the absence of significant π-π stacking interactions in both the n-octane and cyclohexane gels of L-PheN6, with only hydrogen bonds (19.87° and 19.62°) being observed. This contrasts sharply with the P-helical chirality of L-PheO6 n-octane gels, which exhibit a similar interaction pattern dominated by hydrogen bonds. Based on these observations, we hypothesize that the inversion of supramolecular chirality is more readily achieved in L-PheO6 gels due to their relatively limited hydrogen bond interactions, which render the assembly more susceptible to solvent-induced effects. The multiple hydrogen bonds in the L-PheN6 molecule enhance polar interactions between gelator molecules while restricting the apolar interactions of other structural groups within L-PheN6. This structural stabilization renders the aggregates less susceptible to solvent effects, thereby maintaining consistent helical chirality across two diverse weakly polar solvent systems.
Complementarily, FTIR spectroscopy was employed to characterize the hydrogen bonds evolution of both gelator systems in distinct solvent environments (Fig. 2f). The -NH and -CO vibrational modes of L-PheO6 exhibited marked bathochromic shifts in distinct solvents, indicative of solvent-dependent hydrogen bonds reorganization. Notably, the L-PheO6 cyclohexane gel exhibited -NH stretching vibrations at 3343 cm-1 with carbonyl (-CO) modes at 1736 and 1655 cm−1. Conversely, its n-octane counterpart showed a bathochromic shift in -NH vibrations (3291 cm−1) accompanied by altered carbonyl signatures (1734 and 1641 cm−1) (Fig. 2f). This bathochromic evolution demonstrates enhanced hydrogen bonds strength in L-PheO6 gel of n-octane46. In contrast, L-PheN6 maintained consistent vibrational signatures across both solvents, as NH at 3293 cm−1 in cyclohexane and 3290 cm−1 in n-octane, while carbonyl vibrations showed slight shifts from 1716 to 1719 cm−1 and from 1642 to 1643 cm−1. Such spectral invariance suggests L-PheN6 exhibits similar assembly behaviors in the two different solvents, distinct from the solvent-responsive behavior of L-PheO6. This comparative analysis reveals that hydrogen bonds strength modulates the solvent adaptability of gelator assemblies in apolar solvents.
To elucidate the stereochemical influence of gelator architecture, the D-PheO6 enantiomer was synthesized for comparative analysis of supramolecular chiral properties in the organogel. SEM analysis demonstrated inverted supramolecular helicity between D-PheO6 and L-PheO6, with the D-enantiomer adopting M-helical packing in n-octane versus P-helical organization in cyclohexane (Fig. S15). Spectroscopic evidence confirms that the dominant driven force during self-assembly of PheO6 organogel is sensitive to solvent effect. One plausible hypothesis is that there is only single hydrogen bonds set in PheO6, leading to chiral inversion in supramolecular architectures when processed in dissimilar low-polarity solvents. The enhanced hydrogen bond network as the self-assembly driving force for gelators enables the self-assembly behavior of PheN6 aggregates to be less influenced by apolar solvents, while exhibiting identical supramolecular chirality in two distinct weakly polar solvents.
Effect of achiral tail chains on supramolecular chirality
Following the apolar solvent-mediated modulation of supramolecular chirality in organogels, we systematically examined the role of gelator hydrophobic chains in governing the chiral self-assembly of the gels. L-PheOn derivatives with n = 6, 8, and 10 alkyl chains formed n-octane-based organogels that displayed P-helical supramolecular chirality, as evidenced in Fig. 3a–c. Notably, supramolecular chirality was abolished upon alkyl chain elongation to n = 12 and 14 (Fig. 3d, e). It is hypothesized that the van der Waals interaction between gelators and solvents was enhanced with increasing hydrophobic tail chain length of gelators, which critically disrupts the orientation of intermolecular hydrogen bonds and leads to the disappearance of supramolecular helical chirality. Intriguingly, upon increasing the hydrophobic chain length to n = 16 (Fig. 3f), the gel exhibited a re-emergence of P-helix supramolecular chirality.
a L-PheO6, b L-PheO8, c L-PheO10, d L-PheO12, e L-PheO14, f L-PheO16, g L-PheN6, h L-PheN8, i L-PheN10, j L-PheN12, k L-PheN14, l L-PheN16.
Subsequently, L-PheNn and L-PheOn were retained for comparative analysis to elucidate structural determinants of chiral assembly. The L-PheNn/n-octane gel exhibits P-helical supramolecular chirality at chain lengths n = 6, 8, 10 (Fig. 3g–i), with complete chiral disruption emerging at n = 12, 14 (Fig. 3j, k), which is essentially consistent with L-PheOn. Upon extending the L-PheNn chain to n = 16, supramolecular chirality disappeared (Fig. 3l), which is in contrast to the restored supramolecular chirality observed in L-PheO16.
To further investigate the influence of the gelator’s hydrophobic tail on the self-assembly process, XRD analysis was employed to elucidate the molecular packing arrangement and predominant driving forces governing gel formation (Fig. 4). Figure 3a, b demonstrate that both L-PheOn and L-PheNn exhibit a distinct broad peak at approximately 19.28°–19.98°, indicating that hydrogen bonds is the primary driving force for the self-assembly of these compounds. A pronounced change was observed in the small-angle X-ray diffraction region upon elongation of the molecular tail chain. The small-angle X-ray diffraction patterns of L-PheOn (n = 6, 8, 10, 12, 14) reveal that the interlamellar spacing closely corresponds to the theoretical molecular length, which indicates the formation of monolayer assemblies in the aggregates. However, when n = 16, XRD analysis reveals a marked expansion of the interlayer distance, significantly exceeding the molecular length of organogelators in Fig. 4c. Based on prior evidence11,46,57, we propose that L-PheO16 gel likely adopts an interdigitated bilayer stacking, wherein intermolecular hydrogen bonds induce a novel interdigitated bilayer, thereby driving the re-emergence of supramolecular helical chirality. In contrast, the XRD pattern of L-PheN16 reveals no substantial increase in interlayer distance, with the measured d-value closely corresponding to the molecular dimension of L-PheN16. The observed difference may arise from the enhanced hydrogen bond network in L-PheN16, which rendered the van der Waals interactions between alkyl chains and solvents insufficient to disrupt the existing intermolecular hydrogen bonds among gelators58, thereby preventing the formation of lamellar aggregates observed in L-PheO16 (Fig. 4d).
a L-PheOn in two weakly polar solvents, b L-PheNn in two weakly polar solvents, c XRD and theoretical molecular lengths of L-PheOn, d XRD and theoretical molecular lengths of L-PheNn.
Theoretical calculation
Based on XRD characterization results, computational modeling to investigate the supramolecular assembly mechanisms of self-assembly in gels was employed. First, their geometric conformations were optimized using density functional theory (DFT), with the resulting structures depicted in Fig. S16. Among these compounds, L-PheOn exhibits enhanced flexibility in its hydrophobic terminal chains owing to the presence of a single set of intermolecular hydrogen bonds. This structural feature leads to pronounced morphological diversity in the aggregates formed by L-PheO6 and L-PheO10 by xTB59,60,61. Notably, the tail chains of L-PheO10 demonstrate more compact stacking arrangements compared to the other derivatives (Fig. 5a, b, snapshots from other angles can be found in Fig. S17). In contrast, the aggregates of L-PheN6 and L-PheN10 exhibited minimal structural variation with increasing tail chain length, which can be attributed to the ability of the L-PheNn molecular backbone to form additional intermolecular hydrogen bonds (Fig. 5c, d), which is consistent with the XRD results.
a L-PheO6 with P-helix, b L-PheO10 with P-helix, c L-PheN6 with P-helix, d L-PheN10 with P-helix, e L-PheO16 with P-helix. f L-PheN16 with sheet.
Furthermore, Fig. 5e reveals a distinctive bilayer assembly mechanism in L-PheO16 gels, wherein the hydrophobic alkyl chains mediate lamellar stacking through van der Waals interactions. Intermolecular hydrogen bonds on both lateral sides generate a novel double-layered architecture, leading to supramolecular helical chirality. In contrast, L-PheN16 maintains monolayer aggregation behavior as evidenced in Fig. 5f. The mutually restrictive effects between amide-derived hydrogen bonds networks and van der Waals interactions among elongated hydrophobic tail chains effectively suppress supramolecular helical chirality formation in the gels, which prevents the supramolecular chirality regenerated in L-PheN16 gels as achieved by L-PheO16.
The influence of achiral factors on supramolecular chiral assembly and chirality inversion was investigated using phenylalanine-based organogels, enabling precise control over the supramolecular chirality of L-PheOn gels in low-polarity, achiral environments. Subsequently, gelators with enhanced hydrogen bond interactions (L-PheNn) were successfully constructed, allowing for a comparative analysis between single-set and multi-set hydrogen bond supramolecular aggregates. These findings unequivocally establish the pivotal role of achiral parameters in regulating supramolecular chirality. To elucidate the mechanistic underpinnings of chiral assembly, molecular simulations were employed to model the supramolecular gel system. Computational results demonstrate that multiple achiral factors, including solvent microenvironment, hydrophobic chain length, and hydrogen bond interactions, significantly modulate the self-assembly behavior of molecular aggregates. This theoretical framework provides critical insights for the rational design of chirality-controllable supramolecular materials.
Methods
Synthesis and characterization of organogels
The synthetic route for the organogelators is shown in Fig. S1, and the detailed synthesis method is described in SI 1.1. For all organogelators, the structures were confirmed using 1H NMR (NMR spectra in SI 1.2). All gels were prepared by “heating-cooling” in alkane solvents, and the gels formed in all solvents were white or translucent, as described in SI 1.3 and Fig. S14. Gels were prepared and tested in XRD, FTIR, and scanning electron microscopy (SEM) using the same concentrations of samples.
Preparation process of organogels
The gelation properties of a series of organogelators in several solvents were characterized. The procedure is to heat a mixture containing a certain amount of organogelator and solvent at 120 °C. When a clear solution was formed, it was stopped and automatically cooled to 25 °C and kept warm. The solution is allowed to stand for 20 min to check for gelation.
Preparation process of xerogel
The prepared organogel was transferred to a silicon plate, and the solvent in the organogel was removed under reduced pressure (0.1 mbar, 25 °C) to obtain a xerogel. We found in the experiment that the variation of temperature affects the microscopic morphology of the xerogel, so 25 °C was used as the standard temperature for this work.
Scanning electron microscopy (SEM)
The xerogels were coated with platinum vapor and analyzed on a Hitachi SU-8010 (SU-8000) microscope operated at 5.0 kV.
X-ray diffraction (XRD) measurements
XRD of gels were analyzed using a Rigaku D/MAX-RB instrument. The X-ray beam generated with a rotating Cu anode at the wavelength of Kα beam at 1.5406 Å was directed toward the film edge and scanning was done up to a 2θ value from 1.5–48°, the scan rate was 4°/min.
Data availability
The authors declare that the data supporting the findings of this study are available and included in the article and its Supplementary Information file. Other detailed experimental procedures are listed in the Supplementary Information file. All data are available from the corresponding author upon request.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (Grant No. 21978124) and the Natural Science Foundation of Ningbo (Grant Nos. 2024J009 and 2024J139).
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Y.-P.H. and F.Y. conceived and designed the experiments. W.Z. carried out the experiments and the computational simulation.
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Zhang, W., Yu, F. & He, YP. Supramolecular chiral inversion and regulation of phenylalanine-based organogels in low-polarity achiral solvents. Commun Chem 8, 243 (2025). https://doi.org/10.1038/s42004-025-01650-8
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DOI: https://doi.org/10.1038/s42004-025-01650-8
