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. 2026 Aug 3;17(37):17806–17814. doi: 10.1039/d6sc02603f

Excited-state conformational flexibility enables intrinsic amplification of circularly polarized luminescence

Jia-Nan Jin a,†, Rui-Long Zhang a,†, Rui Liao b,✉, Feng Wang a,✉
PMCID: PMC13449152  PMID: 42569174

Abstract

Achieving intrinsic amplification of circularly polarized luminescence (CPL) through excited-state conformational regulation remains a fundamental challenge in chiral photonic materials. Here, we demonstrate that excited-state conformational flexibility enables intrinsic CPL amplification in supramolecular polymers. A conformationally adaptable luminophore is integrated into a hydrogen-bonded chiral supramolecular polymer, where photoinduced conformational planarization modulates the local intermolecular environment and organization of emissive units. This conformational adaptability enhances chiroptical responses without relying on external photophysical amplification effects. A 35-fold amplification of CPL is achieved, which significantly exceeds the increase in total emission intensity, suggesting that the enhancement originates from intrinsic chiroptical regulation rather than simple brightness modulation. Control experiments and computational analyses reveal that molecular conformational flexibility and supramolecular organization are critical for the photoactivated CPL amplification. These findings establish excited-state conformational flexibility as a molecular design principle for intrinsically photoresponsive chiroptical materials.

Excited-state conformational flexibility amplifies CPL in supramolecular polymers. Photoinduced planarization reorganizes emissive units, enabling 35-fold CPL enhancement and establishing a design principle for photoresponsive chiroptical materials.graphic file with name d6sc02603f-ga.webp

Introduction

Circularly polarized luminescence (CPL) provides a unique platform for translating molecular chirality into macroscopic optical responses, where chiroptical properties are dictated by the interplay between molecular structures, supramolecular organization, and excited-state electronic interactions.1–7 Although supramolecular assembly has been widely exploited to amplify molecular chirality,8–15 achieving efficient conversion of subtle molecular structural variations into macroscopic chiroptical gain remains fundamentally challenging. In particular, the relationship between excited-state conformational dynamics and chiroptical regulation within supramolecular architectures has yet to be fully elucidated.

Photoexcitation has been widely employed to modulate the optical properties by inducing symmetry breaking, conformational planarization, or redistribution of electronic density within individual chromophores.12,16–20 However, such excited-state structural transformations are inherently transient and localized, and their translation into persistent supramolecular chiroptical responses requires effective coupling with the surrounding molecular environment. Most reported photoactivated CPL systems achieve signal enhancement through extrinsic mechanisms, including oxygen depletion or suppression of non-radiative decay processes,21–24 which primarily increase emission efficiency rather than directly regulate the structural origins of chiroptical amplification. Consequently, the observed increase in CPL intensity is often accompanied by enhanced brightness;22,24 however, it does not necessarily indicate strengthened chiral exciton coupling or optimized dipole–dipole orientation. Therefore, developing intrinsic strategies that utilize molecular conformational adaptability to bridge excited-state structural changes and supramolecular organization represents an appealing approach toward dynamic chiral photonic materials.

Here, we demonstrate that excited-state conformational flexibility enables intrinsic amplification of circularly polarized luminescence in supramolecular polymers. Specifically, compound (R)-1 (Scheme 1) was designed by integrating a conformationally adaptable luminophore16,25–27 with hydrogen-bonding amide motifs, which facilitate the formation of chiral supramolecular polymeric assemblies. Upon photoactivation, the embedded luminophore undergoes partial conformational planarization in the excited state, allowing transient molecular structural changes to be accommodated within the supramolecular environment. Such conformational adaptation modulates intermolecular interactions and the arrangement of emissive units, enabling intrinsic enhancement of chiroptical responses beyond simple emission amplification.

Scheme 1. Schematic illustration of excited-state conformational flexibility enabling intrinsic amplification of circularly polarized luminescence in (R)-1 supramolecular polymers. The chemical structures of the designed compound (R)-1 and the control compounds (R)-2 and 3 are shown in the frame.

Scheme 1

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The resulting supramolecular polymers exhibit a 35-fold enhancement of CPL, which significantly exceeds the increase in total emission intensity, confirming intrinsic amplification of chiroptical output beyond simple brightness enhancement. Control experiments using the conformationally rigid analogue (R)-2 (Scheme 1) and the ester derivative (R)-4 (Scheme S1) demonstrate that molecular flexibility and hydrogen-bond-driven supramolecular organization are indispensable for achieving efficient CPL amplification. These findings establish excited-state conformational flexibility as a molecular design principle for regulating chiroptical responses in dynamic supramolecular materials and provide a strategy for translating molecular-level structural adaptability into macroscopic optical functions.

Results and discussion

Formation of hydrogen-bonded chiral supramolecular polymers

A well-defined chiral supramolecular architecture is essential for regulating the organization of emissive units and translating molecular-level structural changes into macroscopic chiroptical responses. Therefore, the formation of ordered supramolecular polymers with sufficient structural adaptability represents an important foundation for exploring photoinduced CPL amplification. Specifically, compound (R)-1 was designed to integrate a conformationally adaptable luminophore with hydrogen-bonding amide motifs, enabling the formation of chiral supramolecular assemblies through directional intermolecular interactions.

To evaluate the supramolecular assembly behaviour of (R)-1, we first investigated its aggregation behaviour in solution. In CHCl3 (c = 100 µM), (R)-1 exhibited three characteristic absorption bands at 266, 331, and 420 nm (ε: 2.7 × 104, 7.2 × 103, and 3.2 × 103 L mol−1 cm−1, respectively, Fig. 1a). DFT calculations assigned the high-energy absorption bands (266 and 331 nm) to localized π–π*/n–π* transitions within the thianthrene–isoindoline-1,3-dione framework, while the low-energy band at 420 nm was attributed to an intramolecular charge-transfer (ICT) transition from the folded thianthrene donor units to the phthalimide acceptor (Fig. S1, SI).28–30 The absence of a Tyndall effect indicates that (R)-1 exists predominantly in a molecularly dissolved state in CHCl3 (Fig. S2a). When switching to apolar methylcyclohexane (MCH), the emergence of a pronounced Tyndall effect indicated the formation of supramolecular assemblies. The concomitant blue shifts of the absorption bands to 261, 321, and 404 nm (Fig. 1a) further supported the formation of aggregated structures. Gelation experiments additionally revealed a critical gelation concentration (CGC) of 8 mg mL−1 (Fig. S3).

Fig. 1. (a) UV-vis (top) and CD spectra (bottom) of (R)-1 in CHCl3 and MCH (c = 100 µM, 298 K). (b) Experimental (circles) and simulated (lines) cooling curves of the supramolecular polymerization of (R)-1 at three different concentrations (c = 80 µM, 100 µM, 120 µM in MCH). The curves are shown with a 0.1 offset in αagg for each next concentration. (c) AFM image of (R)-1 [spin-coating the MCH (c = 100 µM) solution on mica]. (d) IR (top) and VCD (bottom) spectra of (R)-1 gels in MCH. (e) CD spectra of the 10 wt% (R)-1 and (S)-1 PMMA film.

Fig. 1

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The thermodynamic characteristics of the supramolecular polymerization were further investigated by temperature-dependent UV-vis spectroscopy in MCH (c = 100 µM). Heating to 343 K resulted in an absorption spectrum identical to that of the monomeric state in CHCl3 (Fig. S4a), confirming reversible disassembly into molecularly dissolved species. Monitoring the absorption intensity at 275 nm during cooling revealed a cooperative nucleation–elongation profile (Fig. 1b). The critical elongation temperature (Te) and cooperativity factor (σ) were determined to be 301.9 K and 1.39 × 10−4, respectively (Table S1). Fitting with a one-component equilibrium model afforded an elongation free energy (ΔGe) of −25.4 kJ mol−1 (Table S1) and an average degree of polymerization 〈Nn〉 exceeding 100 at 293 K (Fig. S5). These results demonstrate the formation of ordered supramolecular polymers capable of maintaining extended molecular organization. AFM imaging revealed micrometre-long nanofibers with an average height of 5.1 nm (Fig. 1c and S6), while TEM measurements further confirmed the fibrous morphology (Fig. S7a).

We next investigated the chiral organization of the supramolecular polymers. At 343 K, no detectable CD signal was observed in MCH, consistent with the molecularly dissolved state (Fig. S4b). Upon cooling below Te (301.9 K at c = 100 µM), two positive CD bands gradually emerged at 350 and 297 nm, indicating the development of supramolecular chirality through assembly (Fig. 1a and S4b). Under identical conditions, the enantiomer (S)-1 displayed mirror-image CD responses (Fig. 1a). These results demonstrate efficient transfer of molecular chirality from the stereogenic centre to the π-conjugated framework during supramolecular polymer formation, establishing a chiral environment for regulating emissive organization.4,31

The intermolecular interactions responsible for supramolecular polymer formation were further examined by FT-IR and VCD spectroscopy. FT-IR spectra of aggregated (R)-1 exhibited characteristic bands at 3292 and 1633 cm−1, corresponding to N–H and C Created by potrace 1.16, written by Peter Selinger 2001-2019 O stretching vibrations associated with intermolecular hydrogen bonding, in contrast to the free molecular state (3430 and 1653 cm−1, respectively, Fig. S8). VCD measurements revealed characteristic signals between 1620 and 1650 cm−1 associated with amide C Created by potrace 1.16, written by Peter Selinger 2001-2019 O vibrations in the aggregated state (Fig. 1d and S9), suggesting ordered chiral arrangement of hydrogen-bonding motifs. Together, FT-IR and VCD analyses confirm that directional hydrogen bonds establish a well-organized chiral supramolecular framework.32 Importantly, the incorporation of adaptable non-covalent interactions provides a dynamic environment capable of accommodating photoinduced conformational changes of the luminophore.

To investigate whether the chiral supramolecular organization could be retained in solid-state materials, (R)-1 was incorporated into a poly(methyl methacrylate) (PMMA) matrix through co-dissolution in CHCl3 and spin-coating. At low doping concentrations of (R)-1 (1–5 wt%), no CD signals were detected (Fig. S10), indicating molecular dispersion of the chromophore. Increasing the loading concentration to 10 wt% resulted in the emergence of CD features comparable to those observed in solution-phase supramolecular polymers (Fig. 1e). Further increasing the concentration enhanced the CD intensity without altering the spectral profile, reaching saturation at 20 wt% (Fig. S10). These results demonstrate the successful chiral supramolecular organization within processable polymer films. The preservation of ordered chiral assemblies in condensed phases provides a suitable platform for investigating photoinduced modulation of supramolecular chiroptical properties.

Photoactivated intrinsic amplification of circularly polarized luminescence

Having established a hydrogen-bonded chiral supramolecular polymer platform, we next investigated whether the excited-state conformational flexibility of the embedded luminophore could regulate supramolecular chiroptical responses. Rather than simply increasing emission intensity, an effective photoresponsive CPL system should enable intrinsic modulation of chiral optical output through structural adaptation of the emissive environment. Therefore, we examined whether photoactivation could enhance CPL beyond the contribution from conventional photophysical brightness enhancement.

Although (R)-1 and (S)-1 exhibited pronounced supramolecular chirality in the ground state, only weak CPL signals centred around 560 nm were observed in the corresponding solid films (Fig. S11). This discrepancy suggests that the chiral organization established in the ground state does not fully translate into excited-state chiroptical activity, possibly due to suboptimal orientation between the transition dipole moments of the luminophores and the surrounding chiral environment.33–35 Upon irradiation of the 20 wt% (R)-1 film with 365 nm UV light for 30 s, a remarkable enhancement of CPL was observed. The emission maximum slightly shifted from 548 to 553 nm (Fig. 2a), accompanied by 35.1-fold and 19.4-fold increases in CPL intensity and dissymmetry factor (glum), respectively (Fig. 2b, S12b and c). These enhancements significantly exceeded the concurrent increase in total photoluminescence intensity (2.9-fold, Fig. 2a and S12a), demonstrating that photoactivation induces intrinsic amplification of chiroptical output rather than a simple brightness enhancement.

Fig. 2. (a) Emission spectra of the 20 wt% (R)-1 PMMA film before (blue line) and after (red line) irradiation with 365 nm light for 30 s. (b) CPL spectra of the 20 wt% (R)-1 and 20 wt% (S)-1 PMMA films before (blue lines) and after (red lines) irradiation. (c) Rewritable photo-patterning of the 20 wt% (R)-1 film, showing repeated writing, erasing, and rewriting of luminescent patterns under UV irradiation and air exposure. (d) Comparison of the CPL enhancement factor (E) under different conditions (“Air + UV” denotes UV irradiation under air, “Ar” denotes an argon atmosphere without UV irradiation, and “Ar + UV” denotes UV irradiation under an argon atmosphere). (e) CPL spectra of the 20 wt% (R)-2 and 20 wt% (S)-2 PMMA films before (blue lines) and after (red lines) irradiation.

Fig. 2

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To clarify the structural requirements for this photoactivated CPL amplification, control experiments were performed by varying the supramolecular organization. At doping concentrations below 5 wt%, where (R)-1 remains predominantly molecularly dispersed in the PMMA matrix, photoirradiation enhanced emission intensity but failed to generate detectable CPL signals (Fig. S13). Similarly, the ester-based analogue (R)-4, which retains conformational flexibility upon photoexcitation (Fig. S14) but lacks the hydrogen-bonding motifs required for supramolecular organization, exhibited no apparent CPL amplification. These results demonstrate that molecular conformational flexibility alone is insufficient; instead, an ordered supramolecular environment is required to accommodate photoinduced conformational changes and translate them into enhanced chiroptical responses.

The photoactivated CPL state of (R)-1 films was highly reversible. After removal of UV irradiation, the enhanced photophysical parameters gradually recovered to their initial values within 5 min under ambient conditions (Fig. S15a and b). Time-dependent PL measurements further confirmed the gradual relaxation of the photoactivated emission state after cessation of irradiation (Fig. S15c and d). This reversible switching behaviour could be repeatedly achieved over dozens of cycles without observable degradation (Fig. S16), highlighting the dynamic adaptability of the supramolecular system.

Taking advantage of the pronounced and reversible luminescence contrast, we further explored the potential of photoactivated (R)-1 films for dynamic information storage and anti-counterfeiting applications.36–38 A 20 wt% (R)-1/PMMA film was irradiated through a photomask containing the pattern “USTC” using 365 nm UV light for 30 s. After removing the mask, a bright yellow luminescent pattern appeared exclusively in the irradiated regions, while the unexposed areas retained weak background emission (Fig. 2c). The written information could be erased by uniform light exposure, and the original low-emission state was recovered after storage under ambient conditions for 5 min. Multiple write–read–erase cycles could be performed on the same substrate, demonstrating the reversibility and processability of the photoresponsive chiroptical material (Fig. 2c).

To further distinguish structural regulation from conventional photophysical effects, the excited-state properties of (R)-1 films were investigated. In air, (R)-1 exhibits a short emission lifetime of 0.9 ns, whereas the lifetime extends dramatically to 4 ms under an argon atmosphere (Fig. S17), indicating the involvement of long-lived excited states. This behaviour is consistent with related thianthrene-based luminophores28 and is further supported by control experiments using compound 3 (Fig. S18). These results suggest that the photoactivated CPL amplification originates from the interplay between excited-state molecular flexibility and the organized supramolecular environment rather than from simple enhancement of radiative emission.

Excited-state conformational flexibility enables enhanced chiroptical responses

Because oxygen depletion can enhance emission from long-lived excited states, we first evaluated its contribution to the photoactivated luminescence and CPL enhancement of (R)-1 films. Under deoxygenated conditions without photoactivation, the total emission intensity increased substantially (Fig. S19a), whereas the CPL signal remained nearly unchanged (Fig. S19b). These results indicate that oxygen removal mainly promotes radiative emission processes but does not directly enhance the chiroptical response. Therefore, the pronounced CPL amplification observed after photoactivation cannot be attributed solely to oxygen-mediated emission enhancement.

To quantitatively distinguish brightness enhancement from intrinsic chiroptical amplification, we defined an enhancement factor:graphic file with name d6sc02603f-t1.webpwhere I0cpl and I0em represent the CPL and total emission intensities before photoactivation, respectively, while I1cpl and I1em correspond to those after photoactivation.

An E value close to 1 indicates that CPL enhancement mainly originates from increased emission intensity, whereas E > 1 reflects an additional contribution from enhanced chiroptical selectivity beyond brightness variation. In the present system, photoactivation in air produced an E value of 12.14 (Fig. 2d and S12), accompanied by an approximately 19-fold increase in glum. This substantial enhancement indicates that photoexcitation modulates the chiroptical environment of the supramolecular assemblies rather than simply increasing emission efficiency.

To further clarify the intrinsic contribution, CPL measurements were performed under an argon atmosphere. After deoxygenation without photoactivation, E remained below 1, confirming that oxygen removal alone cannot account for the observed CPL amplification (Fig. 2d and S19). Subsequent photoactivation under argon conditions resulted in a 24-fold increase in CPL intensity relative to the non-activated state, while the total emission intensity increased only marginally, giving an E value of 16.37 (Fig. 2d and S20). These results further support that the enhanced CPL response originates from photoinduced regulation of the chiral emissive environment rather than from suppression of non-radiative decay.

To identify the molecular factors responsible for this intrinsic chiroptical regulation, we investigated the role of conformational flexibility using the control compound (R)-2 (Scheme 1). In this analogue, replacement of sulfur by oxygen restricts the conformational freedom of the luminophore and enforces a more rigid molecular geometry in both ground and excited states (Fig. 3b and S21). Although (R)-2 is capable of forming chiral aggregates and exhibits photoinduced emission enhancement (Fig. S22 and S23a), negligible CPL amplification was observed under identical irradiation conditions (Fig. 2e and S23b). The corresponding E values remained substantially lower than those of (R)-1 (1.59 under air + UV, 1.61 under Ar, and 2.34 under Ar + UV; Fig. S23c). These results demonstrate that supramolecular chirality alone is insufficient to achieve efficient CPL enhancement; instead, molecular conformational flexibility within the organized supramolecular environment is essential for converting photoinduced structural changes into enhanced chiroptical responses.

Fig. 3. (a) DFT-optimized ground- and excited-state geometries of the (R)-1 monomer, along with the corresponding HOMO and LUMO distributions. (b) DFT-optimized ground- and excited-state structures of the (R)-2 monomer.

Fig. 3

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Collectively, these observations establish a molecular design principle in which excited-state conformational flexibility enables dynamic regulation of supramolecular chiroptical properties. Upon photoactivation, conformational adaptation of the luminophore within the chiral supramolecular framework provides an effective means to modulate the organization and electronic interactions of emissive units, thereby enhancing CPL beyond simple brightness amplification. This flexibility-mediated regulation connects molecular excited-state dynamics with macroscopic chiroptical responses and highlights the importance of adaptable molecular architectures for developing dynamic chiral photonic materials.

Molecular origin of photoactivated CPL amplification

To understand the molecular origin of photoactivated CPL amplification, we investigated the excited-state conformational behaviour of (R)-1 using DFT and TD-DFT calculations. In the optimized ground state (S0), (R)-1 adopts a folded conformation with dihedral angles of 130.9° between the peripheral aromatic rings and the central π-core (Fig. 3a and S24a). This twisted geometry reduces steric interactions between adjacent aromatic units while maintaining the conformational flexibility of the luminophore. Upon photoexcitation to the S1 state, (R)-1 undergoes conformational adaptation, in which one aromatic segment relaxes toward a more planar geometry (176.8°), whereas the other remains partially twisted (136.6°) (Fig. 3a and S24b). Such excited-state planarization reflects the intrinsic conformational flexibility of the chromophore and provides a molecular basis for regulating its electronic and intermolecular interactions.

Frontier orbital analysis further reveals the electronic consequences of this excited-state conformational adaptation. In the ground state, the HOMO is distributed across the conjugated backbone, whereas the LUMO is mainly localized on the acceptor moiety (Fig. 3a). After excitation, the partial planarization leads to a redistribution of the excited-state electron density, resulting in an asymmetric excited-state electronic configuration (Fig. 3a). This conformationally induced electronic adjustment increases the transition dipole moment and facilitates radiative emission (Fig. S24 and S25), consistent with the enhanced photoluminescence observed experimentally. Meanwhile, the increased π-surface exposure of the planarized segment provides a possible molecular origin for modifying intermolecular interactions within the supramolecular environment.

To further examine how excited-state conformational flexibility may influence the arrangement of emissive units, molecular assemblies consisting of four (R)-1 molecules were computationally evaluated. In the ground-state geometry, the folded monomers adopt a closely packed π-stacking arrangement with an average intermolecular distance of 3.61 Å and hydrogen-bond distances ranging from 1.83 to 1.88 Å (Fig. S26a). This packing geometry favours close stacking but limits helical distortion. Upon applying the excited-state adapted molecular geometry, the optimized assembly exhibits modified intermolecular interactions and altered transition dipole arrangements (Fig. S26b). These calculations suggest that excited-state conformational adaptation can modulate the local intermolecular environment and transition dipole arrangement within the supramolecular assembly.

The influence of this molecular adaptation on emissive interactions was further supported by experimental observations. The excitation spectra of the 20 wt% (R)-1 PMMA film exhibited a variation in the I370/I448 ratio after UV irradiation, increasing from 1.27 to 1.80 (Fig. S27d). This change indicates a photoinduced modification of the excited-state electronic environment, consistent with molecular planarization and altered emissive interactions. Notably, XRD, FT-IR, and VCD measurements revealed no significant structural changes before and after photoactivation (Fig. S27a–c), suggesting that the CPL enhancement does not originate from a large-scale supramolecular phase transition. According to exciton coupling theory,39–41 the chiroptical response is highly sensitive to the relative orientation and distance of transition dipoles. Therefore, subtle modulation of emissive coupling induced by conformational adaptation may contribute to the enhanced CPL response.42–44

The importance of conformational flexibility was further demonstrated using the rigid analogue (R)-2. Replacement of sulfur with oxygen restricts the molecular flexibility of (R)-2, resulting in nearly identical dihedral angles in the ground and excited states (179.7° and 179.8°, respectively, Fig. 3b). Consequently, the excited-state structure of (R)-2 exhibits limited conformational adaptability, and the corresponding supramolecular assembly exhibits limited variation in its excited-state intermolecular interactions after excitation. This reduced structural adaptability correlates with the absence of pronounced CPL amplification despite the formation of chiral aggregates. These comparisons highlight excited-state conformational flexibility as a key molecular parameter for enabling photoactivated chiroptical enhancement.

Taken together, the computational and experimental results reveal a molecular mechanism underlying photoactivated CPL amplification: (i) photoexcitation induces conformational adaptation of the flexible luminophore; (ii) the adapted excited-state geometry modifies electronic distribution and local intermolecular interactions; and (iii) the resulting modulation of emissive interactions enhances the chiroptical response of the supramolecular polymer. This highlights excited-state conformational flexibility as a molecular design principle for regulating CPL in dynamic supramolecular materials and demonstrates how molecular adaptability can be harnessed to achieve intrinsic photoresponsive chiroptical amplification beyond conventional brightness enhancement mechanisms.

Conclusions

In summary, we demonstrate that excited-state conformational flexibility enables intrinsic amplification of circularly polarized luminescence in supramolecular polymers. By integrating a conformationally adaptable luminophore into a hydrogen-bonded chiral supramolecular platform, photoinduced conformational adaptation regulates the emissive environment and enhances chiroptical responses beyond simple brightness modulation. Unlike conventional photoactivated CPL systems relying on extrinsic photophysical effects, the present strategy achieves intrinsic CPL amplification, with the enhancement substantially exceeding the increase in total emission intensity. Computational analysis further reveals that excited-state planarization modulates electronic distribution and intermolecular interactions, providing a molecular basis for the enhanced chiroptical response. These findings establish conformational flexibility as a design principle for intrinsically photoresponsive chiroptical materials.

Author contributions

F.W. and R.L. conceived the idea for this project. J.J. performed the experiments, analyzed the data, and produced the artwork under the direction of F.W. R.Z. contributed to the theoretical calculations. J. J. and R. Z. contributed equally to this work. All authors contributed to the manuscript.

Conflicts of interest

There are no conflicts to declare.

Supplementary Material

SC-017-D6SC02603F-s001

Acknowledgments

This work was supported by the National Natural Science Foundation of China (22371272, 92356302, 22571001 and 22301295) and the Natural Science Foundation of Hefei City (BJ2060200041).

Data availability

The data supporting this article are included in the supplementary information (SI). Supplementary information: experimental procedures, synthetic methods, compound characterization, spectroscopic data, computational details, and supplementary figures. See DOI: https://doi.org/10.1039/d6sc02603f.

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Associated Data

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Supplementary Materials

SC-017-D6SC02603F-s001
SC-017-D6SC02603F-s001.pdf (5MB, pdf)

Data Availability Statement

The data supporting this article are included in the supplementary information (SI). Supplementary information: experimental procedures, synthetic methods, compound characterization, spectroscopic data, computational details, and supplementary figures. See DOI: https://doi.org/10.1039/d6sc02603f.

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