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Shunsuke Imai, Takumi Hamada, Misa Nozaki, [Takatoshi Fujita](https://orcid.org/0000-0003-1504-2249), Mariko Takahashi, [Yasuhiko Fujita](https://orcid.org/0000-0003-1302-1436), [Koji Harano](https://orcid.org/0000-0001-6800-8023), [Hiroshi Uji-i](https://orcid.org/0000-0002-0463-9659), [Atsuro Takai](https://orcid.org/0000-0003-3457-3352), [Kenji Hirai](https://orcid.org/0000-0003-3307-3970)

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[Accessing a Hidden Pathway to Supramolecular Toroid through Vibrational Strong Coupling](https://mdr.nims.go.jp/datasets/3b45ec43-ac1a-4a5a-af6f-2ac672e118e4)

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Accessing a Hidden Pathway to Supramolecular Toroid through Vibrational Strong CouplingAccessing a Hidden Pathway to Supramolecular Toroid throughVibrational Strong CouplingShunsuke Imai,†† Takumi Hamada,†† Misa Nozaki, Takatoshi Fujita, Mariko Takahashi, Yasuhiko Fujita,Koji Harano, Hiroshi Uji-i, Atsuro Takai,* and Kenji Hirai*Cite This: J. Am. Chem. Soc. 2025, 147, 23528−23535 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Control over specific intermolecular interactions iscrucial to the formation of unique supramolecular assemblies.Recently, vibrational strong coupling (VSC) has emerged as a newtool for manipulating these interactions. Although VSC showspromise for controlling molecular assembly, it has not yetdemonstrated the capability to open a pathway for creating structuresthat are inaccessible by conventional assembly methods. Here, weused VSC to control the transformation process of a naphthalene-diimide supramolecular polymer induced by a click reaction. Thesupramolecular polymers with reactive ethynyl groups undergo atransformation from long fibers to thick fibers upon induction by anamino-yne click reaction in the absence of VSC. Under VSC of theC−H stretch, the click reaction within supramolecular polymers isaccelerated; no such acceleration occurs in the reaction of individual monomers, suggesting that the acceleration is due to changes inthe assembled structures. Indeed, applying the VSC to the C−H stretch uniquely altered the morphological transformation process,leading to the formation of metastable toroids instead of thick fibers. Notably, the molecular assembly cannot be directed toward atoroidal structure without a VSC. Theoretical simulations suggested that slipped packing configurations in the supramolecularpolymers form the curvature necessary for toroidal structures. The experimental results, supported by theoretical simulations, suggestthat intermolecular interactions among naphthalenediimide molecules are modified under VSC, leading to a slipped packingconfiguration of the toroidal assembly. These findings link the VSC-induced modulation of intermolecular interactions to structuraloutcomes, establishing VSC as a tool for manipulating molecular assembly beyond traditional assembly methods.■ INTRODUCTIONMolecules with specific intermolecular interactions can formintricate structures, as seen not only in biological systems suchas proteins and the DNA helix but also in synthetic materialssuch as supramolecular polymers1−5 and porous materials.6,7These interactions dictate the assembly process and ultimatelyinfluence the stability and functionality of the resultingstructures. Historically, organic synthesis has enabled theintroduction of specific functional groups into molecularcomponents to tailor intermolecular interactions. In sharpcontrast to conventional organic synthesis, vibrational strongcoupling (VSC) has emerged as a new tool for manipulatingintermolecular interactions.8−13VSC was initially used to control chemical reactions,14−17including organic and enzymatic reactions.18,19 Subsequently,the scope of VSC expanded to influence self-assembly,encompassing systems such as polymer assemblies,20 metal−organic frameworks,21 DNA origami,22 and supramolecules.23Under VSC, assembly behaviors are likely affected by alteredintermolecular interactions among solutes and solventmolecules. This mechanistic hypothesis has recently beensupported by direct observations of changes in Londondispersion forces induced by VSC.24 While VSC showspotential as a tool for controlling molecular assembly, theresulting structures are basically the same as those obtainedthrough conventional assembly methods or depolymerizedmonomers. In other words, the VSC has yet to demonstrate itsunique advantages as a tool for creating assemblies that areinaccessible through conventional assembly processes.Meanwhile, there has been a flourishing development ofsupramolecular polymers that change their nanoscaleassembled structures through chemical reactions.25−30 Thetransformation of assembled structures induced by chemicalreactions suggests that the transformation process can fluctuateunder additional stimuli, leading to the formation of newReceived: February 18, 2025Revised: May 19, 2025Accepted: May 20, 2025Published: May 29, 2025Articlepubs.acs.org/JACS© 2025 The Authors. Published byAmerican Chemical Society23528https://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−23535This article is licensed under CC-BY 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on July 9, 2025 at 07:17:43 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Shunsuke+Imai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takumi+Hamada"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Misa+Nozaki"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takatoshi+Fujita"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mariko+Takahashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yasuhiko+Fujita"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Koji+Harano"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Koji+Harano"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroshi+Uji-i"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Atsuro+Takai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kenji+Hirai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/jacs.5c02960&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/jacsat/147/27?ref=pdfhttps://pubs.acs.org/toc/jacsat/147/27?ref=pdfhttps://pubs.acs.org/toc/jacsat/147/27?ref=pdfhttps://pubs.acs.org/toc/jacsat/147/27?ref=pdfpubs.acs.org/JACS?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/JACS?ref=pdfhttps://pubs.acs.org/JACS?ref=pdfhttps://acsopenscience.org/researchers/open-access/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/assembled structures. We envision that applying VSC tomanipulate intermolecular interactions in such reactive supra-molecular polymers will open new pathways for accessingmetastable assembled structures that cannot be formed byconventional methods.In this study, we employed supramolecular polymersincorporating amino-yne click reaction sites, which enablethe transformation of assembled structures at room temper-ature without the need for a catalyst. By applying VSC duringthis transformation process induced by a click reaction withinsupramolecular polymers, we found that the supramolecularpolymers can settle into previously inaccessible metastablestates, leading to the formation of new assembled structuresunder VSC (Figure 1).■ RESULTS AND DISCUSSIONClick Reaction within Supramolecular Polymersunder VSC. We have developed supramolecular polymersthat undergo a transformation of their assembled structuresinduced by a catalyst-free click reaction.31 The moleculefeatures a naphthalenediimide (NDI) core with ethynyl groupsand long alkyl chains at the imide positions, denoted as NDI-1(Figure 1). Due to hydrogen bonding between amide groups,interactions between alkyl chains, and π−π interactionsbetween the NDI core, NDI-1 spontaneously assembles intosupramolecular polymers, denoted as S(NDI-1) (see Support-ing Information for preparation details). Following fiberformation, the fibers can undergo an amino-yne click reactionbetween the ethynyl group and diethylamine (DEA) to affordan amine monoadduct quantitatively (Figure S1a). Thisprocess changes the interactions among NDIs, resulting inmorphological changes of the supramolecular polymers.Because this transformation process is influenced byinteractions among fibers and solvent molecules, the VSCoffers a potential means to change the transformation.S(NDI-1) was dispersed in a methylcyclohexane (MCH)and toluene mixture (4:1 by volume; 2 mM in the monomerunit) and introduced into the Fabry−Perot (FP) cavity. Thereflection mirrors were fabricated using indium tin oxide(ITO)-coated BaF2, as both ITO and BaF2 are transparent tovisible light but reflective in the infrared (IR) range (FigureS2). This design enables the ITO-coated BaF2 mirrors toreflect IR light but allow real-time monitoring of the clickreaction process in the visible light range.32 In contrast, Au andAl reflect and absorb visible light, which can distort theabsorption peaks.33 Therefore, the ITO is a more suitablechoice for this system (Figure S3).The absorption of C−H stretching vibrations of the alkylgroups of S(NDI-1) and the solvent molecules (MCH/toluene) was observed in the range of 2850 cm−1 and 2950cm−1. By tuning the cavity mode to match the energy of theC−H stretching vibrations, two new peaks appeared at 3000cm−1 and 2815 cm−1, corresponding to the formation of upperand lower polaritons. The observed Rabi splitting of thesepolaritonic states indicates the state of the VSC. A significantRabi splitting of 185 cm−1 was observed, exceeding the fullwidth at half-maximum of the cavity mode (45 cm−1) and thebare C−H stretching absorption (85 cm−1), further suggestingthe VSC state (Figure 2).34Figure 1. Schematic illustration of the transformation of supramolecular polymers in response to a click reaction. The assembly of NDI-1 formssupramolecular polymers. While click reactions typically result in thick fibers, the process under VSC conditions led to the formation of toroids.Figure 2. Fourier transform IR spectra of (a) MCH/toluene solutioncontaining S(NDI-1) and DEA and (b) solution introduced in an FPcavity. The cavity mode was tuned to 2908 cm−1 to achieve VSC.Journal of the American Chemical Society pubs.acs.org/JACS Articlehttps://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−2353523529https://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig2&ref=pdfpubs.acs.org/JACS?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asS(NDI-1) solution (2 mM in monomer unit) was mixedwith a DEA solution (2 mM) and introduced into an FP cavityto carry out the click reaction. Due to the instrumental andsolubility limitations, we fixed the concentration of S(NDI-1)and DEA at 2 mM, but we confirmed that there was negligibleconcentration dependence on the resulting product and itsmorphologies. Typical UV−vis absorption derived fromS(NDI-1) was observed before and immediately after theinitiation of the click reaction, indicating that no significantdissociation to monomeric NDI-1 likely occurred under VSCconditions or by the addition of DEA. As the click reactionprogressed, the π−π* transition band (∼446 nm) decreased,while a charge transfer band (∼600 nm) emerged due to theintroduction of an electron-donating amino group adjacent tothe electron-accepting NDI core (Figure S4). It should benoted that the product is an amine monoadduct only, judgingfrom the UV−vis absorption and 1H NMR spectra (Figures S4and S5). By monitoring the decrease in the π−π* transition,the kinetics of the click reaction were analyzed (Figure 3a,b). Itshould be noted that the spectrum collection is focused on the400−465 nm range to rapidly acquire spectra, which isessential for estimating reaction kinetics. The reaction rateconstant under VSC at 298 K was determined to be 11.1 ± 1.5× 10−2 (M−1 s−1), whereas the reaction rate constant withoutVSC was calculated to be 2.66 ± 0.43 × 10−2 (M−1 s−1), asshown in Figures S6 and S7. Thus, the reaction rate increased4 times under VSC. The cavity mode was scanned around theabsorption range of the C−H stretching vibrations (2800−3200 cm−1), and the reaction kinetics were maximized at thepeak of the C−H stretching absorption (Figure 3c). By varyingthe temperature for the click reaction in the range of 288 and318 K under VSC and non-VSC, the activation enthalpy(ΔH⧧) and activation entropy (ΔS⧧) were also evaluated byEyring plots (Figure 4). The resulting values of ΔH⧧ and ΔS⧧were summarized in Table 1. Since ΔH⧧ under VSC is lowerthan that under non-VSC, this suggests that the relatively lowenergy facilitates the progression of the reaction. Additionally,ΔS⧧ under VSC is also lower than that under non-VSC. Thereduced ΔS⧧ indicates that the molecular degrees of freedomdecrease as the reaction progresses. The changes in both ΔS⧧and ΔH⧧ may be attributed to a slight alteration in theassembled structures.To investigate the effect of VSC on reaction kinetics, weused a different molecule, NDI-2, composed of an ethynyl-attached NDI core and branched alkyl long chains at the imidepositions (Scheme S1 and Figure S8). Unlike NDI-1, NDI-2does not form supramolecular assemblies and remainsdispersed as monomers in solution, as confirmed by UV−visabsorption spectra and dynamic light scattering (DLS)measurements (Figure S9). Nonetheless, NDI-2 can undergoan amino-yne click reaction between an ethynyl group andDEA to afford an amine monoadduct, NDI-2−DEA, asconfirmed by 1H NMR spectra (Figures S1b and S10). Thereaction rate constant under VSC was determined to be 20.2 ±2.5 × 10−2 (M−1 s−1), whereas the reaction rate constantwithout VSC was calculated to be 15.2 ± 0.62 × 10−2 (M−1s−1). The difference in rate constants between VSC and non-VSC conditions is only about 30%. Taking into account thestandard errors in the measurements, VSC provides little to nosignificant improvement in the rate constants. Even though theFigure 3. (a,b) Time-dependent UV−vis absorption spectra ofS(NDI-1) during the click reaction: (a) under VSC conditions of theC−H bond and (b) under non-VSC conditions, measured at timepoints of 2, 4, 6, 8, 11, and 13 min. (c) Click reaction rate constant k(M−1 s−1, red dots) plotted on the IR absorption spectrum of thesolution (black line).Figure 4. Eyring plots of click reactions under VSC (red dots) andnon-VSC conditions (black dots).Table 1. Thermodynamic Parameters: Activation Enthalpy(ΔH⧧), Activation Entropy (ΔS⧧)state ΔH⧧ (kJ mol−1) ΔS⧧ (J mol−1)non-VSC 28.1 −179VSC 21.0 −194Journal of the American Chemical Society pubs.acs.org/JACS Articlehttps://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−2353523530https://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig4&ref=pdfpubs.acs.org/JACS?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ascavity mode was scanned around the C−H stretchingvibrations (2800−3200 cm−1), there was nearly no change inthe reaction rate. These results suggest that VSC does notchange the reactivity of the click reaction itself (Figure S11).Instead, the effect of VSC is likely linked to the change in theassembled structures of S(NDI-1) because the reaction ofmonomers (NDI-2) is not sensitive to VSC. This result isreasonable, as the C−H stretch is not directly correlated withthe click reaction.Emergence of Toroidal Assembly. Since the clickreaction induces a transformation of assembled structures inS(NDI-1), atomic force microscopy (AFM) was performedafter the click reaction to observe the resulting morphologies.35The thick fibers appeared when the cavity mode was detunedfrom the C−H stretch, the same as the typical transformationof S(NDI-1) fibers (Figures 5a,b and S12a−c).31 However,under the VSC of the C−H stretch, the transformation ofS(NDI-1) led to the formation of toroidal structures (Figures5c,d). Although various NDI-based supramolecular structureshave been created for decades, the formation of toroids hadnot been observed before.31,36,37 The toroidal structures wereobtained irrespective of the substrates or spin-coatingconditions (Figure S12). Scanning transmission electronmicroscopy of drop-cast samples further revealed toroidalmorphologies (Figure S13). From these results, it can bededuced that the toroidal structures were formed in solutionrather than during the spin-coating process on substrates. TheAFM image analysis of 70 toroidal structures indicates thatthese toroids have a relatively uniform radius of 447 ± 76 nm(Figure S12c−g), with an average height of 16 nm (Figures 5dand S14a,b). Given that the height of the original fibers ofS(NDI-1) is approximately 2.0−2.5 nm (Figure S14c,d), thetoroids are most likely formed by bundled fibers.The toroids and fibers were analyzed by AFM−IRmeasurements, a technique that combines AFM with IRspectroscopy to achieve high spatial resolution for materialcharacterization, particularly in the IR range. This techniqueenables the detection of molecular vibrations, making it usefulfor studying assembled structures on the nanoscale. Bycomparing the IR absorbance spectra of the toroids and fibers(Figure 6), we observed three distinct features in the toroidalstructures: a shoulder around 1740 cm−1 (C�O asymmetricstretch), a peak at 1650 cm−1 (C�O symmetric stretch), andbroadening around 1300−1400 cm−1 (C−H bending). Thesecharacteristic features suggest that the stacking of NDI coresand CH−CH alkyl interactions differs between toroids andfibers.To further investigate the influence of VSC on theassembled structures, we conducted a click reaction forS(NDI-1) in a deuterated solvent mixture of MCH-d14/toluene-d8 (4:1 by volume). In an MCH/toluene mixture (4:1by volume), the C−H stretching vibrations of S(NDI-1),MCH, and toluene are cooperatively coupled to a cavity mode.As a result, the effect of the VSC on NDI-1 and the solventmolecules cannot be discussed separately. However, the C−Hstretch of S(NDI-1) around 2920 cm−1 does not overlap withthe vibrational bands of MCH-d14 and toluene-d8 (FigureS15); thus, the effect of VSC only on solvent molecules can beobservable in deuterated solvents. In deuterated solvents,fibrous structures were observed after the click reactionbetween S(NDI-1) and DEA, even under the VSC of theC−D stretch (Figure S16). This result suggests that thestructural transformation into toroidal assemblies is primarilyattributed to the effect of the VSC on NDI-1 rather than onlyon the solvent molecules. In other words, VSC likely modifiesthe interactions among NDI-1 molecules, leading to a distincttransformation pathway that favors the formation of toroidalstructures.To elucidate the mechanism behind the formation oftoroidal structures, theoretical simulations were performed topredict the stable packing states of the reaction product(denoted as NDI-1−DEA) in supramolecular structures. Thetransformation of these supramolecular structures occurredunder the VSC conditions. After the reaction-inducedtransformation, the solution was extracted and spin-coatedonto a silicon substrate to obtain AFM images. The presenceof toroidal structures on silicon substrate means that theresulting toroidal structures are relatively stable, even underambient conditions. Indeed, the toroidal structures remainedFigure 5. AFM height images of supramolecular polymers: (a) beforethe click reaction, (b) 60 min after the reaction initiation under non-VSC conditions, and (c) 60 min after the reaction initiation underVSC conditions. The reaction solution was diluted 10-fold, and it wasspin-coated onto a silicon substrate. (d) Height profile of a typicaltoroidal structure along the white dotted line in the AFM image.Figure 6. AFM−IR spectra of fibers (black) and toroids (red). Thespectra represent averages of four measurement points.Journal of the American Chemical Society pubs.acs.org/JACS Articlehttps://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−2353523531https://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig6&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig6&ref=pdfpubs.acs.org/JACS?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asunchanged after being kept under ambient conditions forseveral months or heated up to 333 K (Figure S17). Thus, thestable packing structures of NDI-1−DEA dimers werepredicted using DFT with B3LYP-D338/6−311++G(d,p) inGaussian 1639 and PM6-D3H440,41 in MOPAC201642 (seeSupporting Information for details). The interaction betweenNDI-1−DEA is primarily driven by hydrogen bondingbetween amide groups, π−π interactions involving NDIunits, and packing of alkyl chains. Simulations have proposedthree distinct stable packing states for the NDI-1−DEA dimers(entries-2, -3, and -4; Figures S18 and S19 and Table S1). Inentry-2, six alkyl chains extend directly above the NDI cores,obstructing further stacking of NDI-1−DEA and therebyhindering the formation of assembled structures. In contrast,entries-3 and -4 represent plausible stable configurations thatare suitable for discussing the assembly of NDI-1−DEA(Figure 7).In entry-3, the NDI cores stack face-to-face, but in entry-4,the NDIs adopt a slightly slipped stacking configuration.Notably, the slipped stacking configuration in entry-4 forms adihedral angle of 14.24° (γ in Table S1), which contributes tothe curvature required for the formation of toroidal assemblies.The structural extension derived from the simulated NDI-1leads to a one-dimensional assembly in entry-3 and a curvedassembly in entry-4 (Figures 7c,d). These structuralconfigurations suggest that entry-3 and entry-4 serve as thecore assembled frameworks for fibers and toroids, respectively.While nothing definitive can be concluded at this stage, we arecurrently considering the following mechanisms based on ourobservations. The amine addition to S(NDI-1) fibers initiates atransformation process in which curved NDI stackingassemblies give rise to shorter bundled fibers, ultimatelyleading to the formation of toroids under VSC. A secondarynucleation process may also play a significant role in theformation of these toroids, which are several hundrednanometers in diameter.43Another unique feature of entry-4 is the dihedral angle ofNDI, which makes the space around the ethynyl groups moreaccessible to DEA. Comparing the reaction kinetics betweenmonomers of NDI-2 and supramolecular polymers of S(NDI-1), the monomers of NDI-2 exhibit faster reaction kineticsthan the supramolecular polymers of S(NDI-1). This differ-ence arises from the increased steric hindrance at the ethynylreactive sites in the stacked structures in the supramolecularpolymers of S(NDI-1). The steric hindrance restricts theaccessibility of amines to the ethynyl groups of S(NDI-1),slowing the reaction. In this work, under VSC, the clickreaction within supramolecular polymers of S(NDI-1) wasaccelerated, whereas no acceleration was observed inmonomers of NDI-2. This result can be explained by thespace around the ethynyl groups in entry-4, as the reducedsteric hindrance in the supramolecular polymers under VSCpromotes a faster click reaction. This acceleration wasobserved only in the supramolecular structures, explainingwhy the click reaction of NDI-2 monomers was unaffected byVSC. These theoretically predicted stable configurations alsoprovide hypothesized reasoning for the accelerated reactionswithin supramolecular polymers and the formation of toroidalstructures.The predicted structures of entry-3 and entry-4 align wellwith the AFM−IR spectra. In the toroidal assembly, thedihedral angle between the two NDI cores causes the C�Obond, farther from the hydrogen atom, to be positioned on oneside. The presence of weak hydrogen bonds in some diimidesresults in a shoulder at 1740 cm−1 on the high-frequency side.Similarly, due to the dihedral angle, the C�O bond closer tothe hydrogen atom is positioned on the opposite side. Stronghydrogen bonds in some diimides produce a peak at 1650cm−1 on the low-frequency side. Additionally, the tilted overlapof the NDI molecules, induced by the dihedral angle, leads tovarious C−H states both inside and outside the ring, causingthe observed broadening around 1300−1400 cm−1.Additionally, the experimentally observed changes in ΔH⧧and ΔS⧧ under VSC can be rationalized based on the predictedpacking structures. In entry-4, the slipped configuration allowsfacile access of DEA to the ethynyl group, facilitating easieraccess of DEA to the ethynyl group, leading to a lower ΔH⧧under VSC. Furthermore, the enthalpy of the slipped stackingconfiguration in entry-4 is likely higher than that of the face-to-face configuration in entry-3. Since the initial entropy underVSC is higher, the entropy changes during the click reactioncan be more pronounced under VSC compared to those undernon-VSC conditions.The proposed structures can align with the effects of theVSC reported in previous studies. Under the VSC of the C−Hstretching mode, the London dispersion forces between alkylgroups weaken, as observed by changes in the 1H NMRspectra.24 This reduced interaction between alkyl groups hasalso been identified in porphyrin supramolecular polymers,manifested as lower thermal stability at elevated temperatures.The simulation of packing structures in this work also suggeststhat the alkyl interactions in entry-4 are weaker due to theslipped stacking configurations of NDI-1−DEA. This reducedinteraction correlates with the calculated lower stability ofentry-4. Considering previous studies, it is plausible that theFigure 7. Optimized structures of NDI-1 dimers: (a) entry-3 and (b)entry-4. Carbon, hydrogen, oxygen, and nitrogen atoms arerepresented in green, white, red, and blue, respectively. Brown dottedlines denote the planes of the NDI cores. The dihedral angles ofentry-3 and entry-4 are calculated to be 1.45° and 14.24°,respectively. Due to the tilted angles of adjacent NDI cores inentry-4, there is increased spacing between adjacent ethynyl groups(black dotted circles), facilitating click reactions. Using atomiccoordinates from DFT calculations, assembled structures weremodeled by repeating the dimer unit. Illustrative diagrams of theassembled structures corresponding to entry-3 and entry-4 are shownin (c) and (d), respectively. The near-planar NDI cores in entry-3lead to fiber-like assemblies, while the larger dihedral angle in entry-4promotes the formation of toroidal structures.Journal of the American Chemical Society pubs.acs.org/JACS Articlehttps://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−2353523532https://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig7&ref=pdfhttps://pubs.acs.org/doi/10.1021/jacs.5c02960?fig=fig7&ref=pdfpubs.acs.org/JACS?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asVSC of the C−H stretch in solvent molecules and the alkylgroups of NDI-1 induce weaker CH−CH interactions. This, inturn, facilitates the formation of entry-4, disclosing the uniquetoroidal assemblies herein.■ CONCLUSIONSThis work demonstrates the potential of VSC to manipulatemolecules into unique assembly structures. The self-assembledfibers, stabilized by hydrogen bonding, π−π interactions, andalkyl chain interactions, underwent transformations ofassembled structures upon the click reaction, which introducedtertiary amino groups into the assembly. Remarkably, the VSCof the C−H stretch significantly altered these transformations,leading to unique toroidal structures. Under VSC, reactionkinetics were enhanced compared to non-VSC conditions, asevidenced by a decrease in the π−π* transition band and theemergence of a charge transfer band in the UV−vis absorptionspectra. The observed acceleration of reaction kinetics underVSC was specific to the supramolecular polymers, with nearlyno enhancement detected for monomeric NDI-2, highlightingthe dependence of VSC effects on assembled states. Thissuggests that the VSC influences the interplay of molecularinteractions within the assembly.AFM revealed a striking difference in the final structuresformed under VSC. Unlike the thick fibers typically observedafter the click reaction, VSC uniquely facilitated the formationof toroidal structures. Simulations provided insights into theplausible stacking configurations, showing that the weakenedalkyl interactions and slipped packing create a curvature,enabling toroidal assembly. This configuration, with reducedsteric hindrance around reactive sites, likely explains theenhanced reaction kinetics under the VSC.The findings establish a link between the VSC-inducedmodulation of intermolecular interactions and the structuraloutcomes in supramolecular systems. By modulating inter-molecular interactions and promoting alternative packingconfigurations, the VSC emerges as a unique tool tomanipulate molecular assembly. These insights not onlyexpand the understanding of VSC in complex molecularsystems but also open avenues for creating assembledstructures that are inaccessible through conventional methods.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/jacs.5c02960.Materials and methods, additional control experiments,and details of theoretical simulations (PDF)■ AUTHOR INFORMATIONCorresponding AuthorsAtsuro Takai − Molecular Design and Function Group,National Institute for Materials Science (NIMS), Tsukuba,Ibaraki 305-0047, Japan; orcid.org/0000-0003-3457-3352; Email: TAKAI.Atsuro@nims.go.jpKenji Hirai − Division of Photonics and Optical Science,Research Institute for Electronic Science (RIES), HokkaidoUniversity, Sapporo, Hokkaido 001-0020, Japan; Division ofInformation Science and Technology, Graduate School ofInformation Science and Technology, Hokkaido University,Sapporo, Hokkaido 060-0814, Japan; orcid.org/0000-0003-3307-3970; Email: hirai@es.hokudai.ac.jpAuthorsShunsuke Imai − Division of Photonics and Optical Science,Research Institute for Electronic Science (RIES), HokkaidoUniversity, Sapporo, Hokkaido 001-0020, Japan; Division ofInformation Science and Technology, Graduate School ofInformation Science and Technology, Hokkaido University,Sapporo, Hokkaido 060-0814, JapanTakumi Hamada − Molecular Design and Function Group,National Institute for Materials Science (NIMS), Tsukuba,Ibaraki 305-0047, Japan; Department of Materials Scienceand Engineering, Faculty of Pure and Applied Sciences,University of Tsukuba, Tsukuba, Ibaraki 305-8577, JapanMisa Nozaki − Institute for Quantum Life Science, NationalInstitutes for Quantum Science and Technology, Inage, Chiba263-8555, JapanTakatoshi Fujita − Institute for Quantum Life Science,National Institutes for Quantum Science and Technology,Inage, Chiba 263-8555, Japan; orcid.org/0000-0003-1504-2249Mariko Takahashi − Research Institute for SustainableChemistry, National Institute of Advanced Industrial Scienceand Technology (AIST), Higashihiroshima, Hiroshima 739-0049, JapanYasuhiko Fujita − Research Institute for SustainableChemistry, National Institute of Advanced Industrial Scienceand Technology (AIST), Higashihiroshima, Hiroshima 739-0049, Japan; orcid.org/0000-0003-1302-1436Koji Harano − Center for Basic Research on Materials,National Institute for Materials Science (NIMS), Tsukuba,Ibaraki 305-0044, Japan; Research Center for AutonomousSystems Materialogy (ASMat), Institute of IntegratedResearch, Institute of Science Tokyo, Yokohama, Kanagawa226-8501, Japan; orcid.org/0000-0001-6800-8023Hiroshi Uji-i − Division of Photonics and Optical Science,Research Institute for Electronic Science (RIES), HokkaidoUniversity, Sapporo, Hokkaido 001-0020, Japan; Division ofInformation Science and Technology, Graduate School ofInformation Science and Technology, Hokkaido University,Sapporo, Hokkaido 060-0814, Japan; Department ofChemistry, KU Leuven, Heverlee, Leuven 3001, Belgium;Institute for Integrated Cell-Material Science (WPI-iCeMS),Kyoto University, Kyoto 606-8317, Japan; orcid.org/0000-0002-0463-9659Complete contact information is available at:https://pubs.acs.org/10.1021/jacs.5c02960Author Contributions††S.I. and T.H. are contributed equally.NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSWe express our gratitude to Izumi Matsunaga (NIMS) andNobuko Maeizumi (Hokkaido University) for their assistancein various experiments. We also acknowledge Dr. YoshihiroYamauchi for allowing us to use a DLS instrument. This workwas supported by JSPS KAKENHI Grant NumbersJP23H04877, JP24H01734, JP23H04879, and JP23H04874in a Grant-in-Aid for Transformative Research Areas “MaterialsScience of Meso-Hierarchy.” We thank the Open Facility,Global Facility Center, Creative Research Institution, andHokkaido University for allowing us to conduct AFM. We alsoJournal of the American Chemical Society pubs.acs.org/JACS Articlehttps://doi.org/10.1021/jacs.5c02960J. Am. Chem. Soc. 2025, 147, 23528−2353523533https://pubs.acs.org/doi/10.1021/jacs.5c02960?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/jacs.5c02960/suppl_file/ja5c02960_si_001.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Atsuro+Takai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-3457-3352https://orcid.org/0000-0003-3457-3352mailto:TAKAI.Atsuro@nims.go.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kenji+Hirai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-3307-3970https://orcid.org/0000-0003-3307-3970mailto:hirai@es.hokudai.ac.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Shunsuke+Imai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takumi+Hamada"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Misa+Nozaki"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takatoshi+Fujita"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-1504-2249https://orcid.org/0000-0003-1504-2249https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mariko+Takahashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yasuhiko+Fujita"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-1302-1436https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Koji+Harano"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-6800-8023https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroshi+Uji-i"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-0463-9659https://orcid.org/0000-0002-0463-9659https://pubs.acs.org/doi/10.1021/jacs.5c02960?ref=pdfpubs.acs.org/JACS?ref=pdfhttps://doi.org/10.1021/jacs.5c02960?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asthank ARIM of MEXT (JPMXP1224NM5109 andJPMXP1225NM5064) for NMR usage. 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