Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions

Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions Sung Ho Jung, Hyeon Min Han, Min Joo Kim, Jong Hwa Jung This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6654028/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Designing the organization of supramolecular systems with high-precision self-assembly along diverse pathways is a crucial strategy for optimizing functional properties. However, attaining this degree of control remains a significant challenge in the field. Here, we report the selective pathway dynamics of platinum (II) terpyridine-based complexes with (R) -chiral side chains, which exhibit three distinct states (Agg-A, -DH, and -SH) in different pathways during the self-assembly process. Specifically, the Pt-complexes ( R )-1 self-assemble into helical structures with opposite handedness as metastable Agg-A (M-type or P-type) depending on concentrations, which led to selective pathways due to transient helical inversion of Agg-A. Our kinetic experiments clearly demonstrated time- and temperature-dependent pathway dynamics. The kinetic observations at 308 K reveal the presence of a kinetically trapped aggregation (Agg-DH) with a double helix driven by interfiber interaction that forms via a transient helical inversion of metastable state (Agg-A) as an on-pathway intermediate (P-type). At 333 K, a thermodynamically favored aggregation (Agg-SH) with a single helix emerges from the metastable state Agg-A as an off-pathway intermediate. Interestingly, the metastable Agg-A can follow two different pathways depending on temperatures, leading to either Agg-DH or Agg-SH. Eventually, both distinct metastable state (Agg-A) and kinetically trapped state (Agg-DH) transform into thermodynamically stable state (Agg-SH). Furthermore, seeded-living supramolecular polymerization was conducted to demonstrate selective pathway control. This study demonstrates the control over pathway complexity and their unique morphological evolution driven by transient helical inversion, as well as interfiber and intermolecular Pt-Pt interactions. Physical sciences/Chemistry/Supramolecular chemistry/Supramolecular polymers Physical sciences/Materials science/Nanoscale materials/Molecular self-assembly Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Supramolecular polymers, formed by non-covalent interactions between monomeric units through spontaneous self-assembly processes, have emerged as a captivating area of research due to their potential applications in fabricating advanced soft materials with unique properties. 1 – 5 Elucidating these fundamental aspects holds immense promise for the directed design of supramolecular materials with tailored functionalities. 6 , 7 The supramolecular stacking arrangements significantly impact their material properties as exhibited in solution or bulk states, influencing phenomena such as gel formation and protein aggregation. 8 , 9 For instance, a comprehensive understanding of disorders linked to protein aggregation from proteins converting into their amyloid forms, such as Alzheimer’s and Parkinson’s diseases, is a fundamental prerequisite for deciphering the pathway complexity involved in aggregation networks. 10 – 12 Therefore, programming the organization of supramolecular systems through high-precision self-assembly along diverse pathways is a key strategy for optimizing functional properties. However, achieving this level of control remains a challenging requirement in the field. By understanding the well-established mechanisms of supramolecular polymerization in recent years, such as isodesmic or cooperative models, remarkable control over supramolecular polymerization was achieved by gaining deep insights into the thermodynamics and kinetics of these processes. 13 – 15 Since the report by Meijer and coworkers on pathway complexity of π -conjugated SOPV in supramolecular polymerization, on- and off-pathway intermediates with helical inversion were proved by kinetic analysis. 16 Such supramolecular interactions in these materials are dynamic, allowing a single monomeric molecule to follow diverse pathways in multiple aggregation processes. These materials can be engineered to exhibit sensitivity to the chemical reaction and respond to a chiral environment. 17 – 24 Understanding the kinetics of the pathway complexity is crucial, as it governs the self-assembly processes. Pathway complexity in supramolecular polymers serves as a powerful benchmark for mimicking the natural processes of biomolecules, facilitating the creation of intricate, functional structures. 25 – 28 Despite its significance, the kinetics of chirality evolution in natural systems remains poorly understood, continuing to captivate researchers from various disciplines. Unraveling these kinetic processes is essential for advancing the field of supramolecular polymerization and its applications in creating sophisticated materials. 19 , 29 , 30 To date, rational strategies for control over pathways in self-assembly have primarily relied on molecular design, competition between inter and intramolecular hydrogen bonding, dynamic covalent bonds, and the self-assembling protocol. 31 – 40 However, exploiting pathway complexity driven by helical inversion with metal-metal interaction to tune self-assembly processes in time evolution is rare and considerably more challenging. We are particularly interested in the self-assembly of Pt complexes, a class of chromophores that is of interest for ap-plications owing to their outstanding photophysical prop-erties. 41 – 43 In our earlier work, we showed dynamic self-assembling behavior with helical inversion and circularly polarized luminescence (CPL). 44 Although the photophysical properties and self-assembly behaviors of supramolecular polymers derived from Pt(II) complexes have been extensively studied by our group 45 and others, 46 , 47 the selective pathways and transient helical inversions occurring during supramolecular polymerization have not yet been investigated. By introducing steric effects of the biphenyl group and alkyl chain in molecular design, we achieved the revealing of the self-assembling pathways of the Pt complex in supramolecular polymerization with unique time evolution. Herein, we have presented the kinetically controlled self-assembly of Pt complex ( R or S )-1 into the single and double helix structures via transient helical inversion in supramolecular polymerization with time evolution, which unprecedented kinetic behavior (Scheme 1 ). The detailed helical inversion in selective pathway dynamics, along with its unique time evolution, was investigated using circular dichroism (CD) spectroscopy. The activation energy for the transient helical inversion from M -type to P -type aggregates in the metastable state was determined through temperature-dependent CD observations. Distinct morphological differences between kinetically trapped aggregates and thermodynamic aggregates were observed through scanning electron microscopy (SEM) and atomic force microscopy (AFM). Although the time-dependent evolution appeared complex, we successfully demonstrated the pathway complexity of controllable aggregation pathways through temperature programming. Thermodynamic studies were conducted to evaluate the stability of both kinetic and thermodynamic aggregates. Furthermore, seeded living supramolecular polymerization was utilized to control selective pathway dynamics. Results Molecular design and synthesis. In this study, terpyridine-based Pt(II) complexes 1 possessing R - or S -enantiomeric alanine moiety were designed with unsaturated fatty acid containing a chiral amide group at one terminus and a biphenyl group and alkyl chain at the other. The molecular design derived from a previously reported monomer (chloroplatinum (II) complex) (Supplementary Scheme 1), known to form helical supramolecular tubes as a consequence of enhanced chiroptical properties, including circularly polarized luminescence generated through a unique dynamic morphological transformation and helical inversion. In this study, we focused on modulating π - π and Pt-Pt interactions in supramolecular polymerization by introducing an alkyne ligand. Specifically, substituents were incorporated to investigate the dynamic self-assembly process in supramolecular polymerization, which has been extensively studied for its tunable optical and electronic properties. 45 – 47 Thus, the previously reported chloroplatinum (II) complex was coordinated with alkynyl ligands, such as the biphenyl group and alkyl chain, and we obtained the structures of ( R )-1 . Complexes ( R and S ) -1 were synthesized according to synthetic pathways, as shown in Scheme S1 in the supporting information. All the complexes have been characterized by 1 H and 13 C NMR, FT-IR, elemental analysis, and HS-ESI mass spectrometry. Aggregation pathway from Agg-A to Agg-DH with helical inversion. The supramolecular polymerization was demonstrated through their aggregation pathway in a mixture of dimethyl sulfoxide (DMSO) and water. In this system, the complex ( R )-1 was molecularly dissolved in DMSO at 293K, allowing us to study the dynamic self-assembly process across a broader range of concentrations using a solvent mixing protocol with water. Initially, the self-assembling behavior of complexes ( R )-1 in a mixture of DMSO and water was investigated by circular dichroism (CD) and UV-Vis spectroscopy. Notably, when a DMSO solution of monomeric ( R )-1 was rapidly injected into the water, we could observe the concentration-dependent helical inversion of aggregated ( R )-1 (in the following denoted Agg-A) (Fig. 1 ). The final solvent of DMSO: water ratio was 6:4, and the resulting ( R )-1 concentrations ranged between 125 µM and 400 µM. Upon increasing the concentration of Agg-A at 293K, the nega-tive Cotton CD signal at 293 nm increased up to 200 µM, while the corresponding positive Cotton CD signal in-creased at 400 µM, which strongly indicated that helical inversion of Agg-A from P-type (right-helicity) to M-type (left-helicity) occurs depending on the concentration of ( R )-1 , as evidenced by the mirror-image of ( S )-1 with Cotton effect (Fig. 1 and Supplementary Fig. 1). In the UV-Vis spectra of Agg-A in a mixture of DMSO and water (6:4, v/v), the high-energy absorption band in 270–350 nm decreased, while a lower-energy band in the 370–500 nm range, assignable to metal-to-ligand charge transfer (MLCT), redshifted to around 470 nm. These observations imply that the intermolecular interactions in assembled Agg-A were mainly assisted by π-π interactions (Supplementary Fig. 2). To further characterize the Agg-A with helical inversion, atomic force microscopy (AFM) analysis was performed. When this solution was spin-coated onto a mica substrate, AFM observation revealed the helical nanofibers (Supplementary Fig. 3). The height of Agg-A in M-type and P-type assemblies was ≈ 12 nm. The right-handed P-type and left-handed M-type helical nanofibers co-existed, respectively. The ratio of right- and left-handed nanofibers depended on the concentration of Agg-A and was consistent with the Cotton effect observed in CD spectra (Supplementary Fig. 3). Interestingly, the CD spectrum of Agg-A composed of ( R )-1 (200 µM) in a mixture of DMSO and water (6:4, v/v) after aging for 1 day showed a significantly different spectral signature with a further increase in the negative CD signal at λ max = 320 nm. Additionally, a weak positive first Cotton effect at 567 nm and a weak negative second Cotton effect at 482 nm corresponding to metal-metal-to-ligand charge transfer (MMLCT) was observed, as characterized by the appearance of an absorption shoulder band at 540 nm (Fig. 1 F and Supplementary Fig. 2). 44 These observations suggest that metastable Agg-A of ( R )-1 transformed into thermodynamically favored aggregates (in the following denoted Agg-DH) via dynamic intermolecular interactions, particularly with enhanced Pt-Pt interaction during supramolecular polymerization. 48 The time-dependent transformation with sigmoidal growth of helical supramolecular polymers (Agg-DH) suggests the possible existence of competing pathways in the self-assembly of ( R )-1 . To get a deeper understanding of the aggregation pathway with a characteristic of the lag phase, kinetic experiments were carried out to evaluate the relationship between helical inversion and concentrations of Agg-A (Fig. 1 and Supplementary Fig. 4). The unique kinetic profiles were observed in the time evolution accompanying the helical inversion of Agg-A, where the resulting kinetic profiles exhibit a sigmoidal growth pattern with a lag phase characteristic of the presence of a metastable state in the supramolecular polymerization, indicating autocatalysis processes. 49 A plot of half-time, t 50 (time at which 50% of the aggregation process) against concentrations, obtained from corresponding time-dependent CD spectra changes, versus corresponding concentration of Agg-A gives V-shaped kinetic profiles with a decrease in the t 50 with closing at 200 µM (Fig. 1 H). At higher concentrations (400 µM), a positive CD signal appeared at 293 nm in the initial stages of the assembly process and then transformed into a negative CD signal (λ max = 320 nm) at later times, suggesting the initial formation of M-type Agg-A as an off-pathway intermediate that then converted into thermodynamically favorable P-type Agg-A as an on-pathway intermediate during time-evolution toward Agg-DH (Supplementary Fig. 5). Note-worthy is that the t 50 is longer at 400 µM than at 200 µM (Fig. 1 F). In contrast, the presence of a more extended lag phase in kinetic profiles at the lowest concentrations (below 200 µM) and an inverted dependence of t 50 on concentration was observed in kinetic studies (Fig. 1 H). This is attributed to the dilution effect, leading to the dissociation process of P-type Agg-A in equilibria between monomer and Agg-A. This concentration dependence indicates that M-type Agg-A is an off-pathway aggregate, and P-type Agg-A is an on-pathway aggregate in transformation for Agg-DH. In conclusion, the supramolecular polymerization of ( R )-1 exhibited a kinetic pathway with helical inversion, as evident from the changes in CD intensity at 320 nm. To clearly investigate the influence of helical inversion from metastable M-type Agg-A to stable P-type Agg-A, changes in CD signal (400 µM, at 345 nm) were monitored as a function of time at different temperatures. The activation energy for helical inversion from M-type to P-type Agg-A was estimated to be 167 kJmol − 1 using an Arrhenius plot (Fig. 1 and Supplementary Fig. 6). This value is sufficient to suppress the helical inversion at 293 K. Additionally, based on the Eyring plot, activation enthalpy (ΔH ≠ ) and entropy (ΔS ≠ ) for helical inversion were 164 kcal mol − 1 and 218 Jmol − 1 K − 1 , respectively (Supplementary Fig. 6). These results indicate that the transient helical inversion of metastable Agg-A contributes to unique time evolution with a lag phase in the transformation into the thermodynamically favored state Agg-DH compared with Agg-A. Therefore, conformational kinetic structures in a transient helical inversion of Agg-A play a critical role in modulating the kinetic pathway in supramolecular polymerization. Morphological transformation from single fiber to double helix. To further investigate the influence of transient helical inversion with unique kinetic profiles on the morphology of the self-assembling characteristics of Agg-A and Agg-DH, we conducted time-dependent scanning electron microscopy (SEM) and atomic force microscopy (AFM). Combined time evolution experiments, along with SEM and AFM imaging using the same solutions, were used to visualize the transformation of Agg-A into Agg-DH at 200 µM. In the lag phage, the metastable Agg-A is characterized by the formation of thin nanofibers of isolated aggregates with a uniform height of 12 nm (Supplementary Fig. 2). Completely discrete double-helix structures were observed by AFM and SEM when the solution of completely transformed Agg-DH. As seen in Fig. 2 , these interacting fibers are intertwined to form right-handed double-helix structures with helical pitches of ∼180 nm and a height of 60 nm (Fig. 2 E). Furthermore, the induction of positive first Cotton CD signals at 570 nm in the region of MMLCT transition of Agg-DH is rationalized by the presence of Pt-Pt interactions of Pt complexes core, inducing intertwined helical arrangement of Pt complexes core of ( R )-1 in the rotational displacement upon transformation (Fig. 2 ). We suggest that the right-handed P-type Agg-A further merge to form right-handed double-helix structures (Agg-DH) via interfiber interaction with Pt-Pt interaction. To understand the reasons underlying unique time evolution with morphological transformation, the MMLCT excited state of Agg-DH was confirmed by the emission spectrum and wide-angle X-ray diffraction (WXRD). In emissive properties, time-dependent PL measurements for ( R )-1 were observed in the same solvent system. Initially, the PL spectrum of Agg-A shows a very weak signal at 695 nm, which increases gradually with aging times (Supplementary Fig. 7). The enhancement of the PL intensity is mainly due to the enhanced Pt–Pt interactions upon the formation of Agg-DH. Additionally, Agg-DH aggregate was studied using wide-angle X-ray diffraction (WXRD). A characteristic Pt-Pt interaction peak at q = 18.7 nm − 1 with a spacing of 0.34 Å was observed (Supplementary Fig. 8). These findings reveal that fibers interact with neighboring fibers, thus supporting the hypothesis that the core of Pt-complex ( R )-1 remains on the fibers’ surface and, together with substituent flexibility, determines higher-order structure formation. These results demonstrate that ( R )-1 undergoes a unique time evolution with pathway complexity, including the morphological transformation from fiber to double-helix structures via interfiber interaction with Pt-Pt interaction. Mechanism of supramolecular polymerization and thermodynamic parameters. Temperature-dependent CD and UV-Vis spectroscopy were performed to gain further insight into the supramolecular mechanism. As shown in Fig. 3 , Agg-A and Agg-DH exhibited clearly distinguishable heating curves. The data from several temperature-dependent CD intensity or UV-Vis absorption changes from 293 to 373 K in DMSO/water (6:4, v/v) at different total concentrations ranging from 100 µM to 250 µM could be fitted with the isodesmic or cooperative model (Supplementary Figs. 9–12). 50 , 51 The sigmoidal heating curve of Agg-A indicated the metastable Agg-A following an isodesmic growth. In contrast, the Agg-DH exhibited a non-sigmodal heating curve with T e (343.5 K), indicating cooperative growth. Through van’t Hoff analysis, the standard enthalpy change (Δ Agg−A H °) and standard entropy change (Δ Agg−A S °) for Agg-A were estimated to be -65 kJ mol − 1 and − 138 J mol − 1 K − 1 , respectively (Supplementary Fig. 10). Additionally, based on a van’t Hoff plot for the elongation process of Agg-DH, the standard enthalpy change (Δ Agg−DH H °) and standard entropy change (Δ Agg−DH S °) for Agg-DH were estimated to be -77 kJ mol − 1 and − 153 J mol − 1 K − 1 , respectively (Supplementary Fig. 12). The more negative standard entropy (ΔS°) of Agg-DH compared to Agg-A suggests that the formation of more organized double-helix structures from single-helix structures via inter-fiber interactions, along with enhanced Pt-Pt interactions, contributes to this increased negative value. As a result, the aggregation of Agg-A and Agg-DH occurs with equilibrium constants of K I =7.0×10 3 M − 1 and K E =1.0×10 5 M − 1 at 308 K, respectively, according to the corresponding propagation models. We realize that Agg-DH, with a larger K E , is the thermodynamic product compared to Agg-A. These results also support that metastable Agg-A eventually transformed into the thermodynamically favored formation of Agg-DH. Additionally, the solution of ( R )-1 was prepared in a mixture of DMSO and water by the cooling process, and no suitable data could be obtained due to a precipitate of ( R )-1 , which resulted in undesired formation during cooling measurements. Consequently, the desired data were obtained through the heating process. Selective pathway under non-equilibrium state. After ultrasonication treatment of metastable Agg-A, the unexpected formation of aggregates (in the following denoted Agg-SH) was obtained, differing from the characteristics observed for Agg-DH in CD and absorption observation (Fig. 4 and Supplementary Fig. 13). The CD spectrum of Agg-SH in a mixture of DMSO and water (6:4, v/v) showed an increase in the negative CD signal at λ max = 310 nm and a weak positive CD signal at 540 nm corresponding to metal-metal-to-ligand charge transfer (MMLCT), in which a characteristic Pt-Pt interaction peak at q = 18.7 nm − 1 with a spacing of 0.34 Å was observed using wide-angle X-ray diffraction (WXRD). (Supplementary Fig. 14). Furthermore, the PL spectrum of Agg-SH revealed an enhanced intensity at 695 nm compared to Agg-A and Agg-DH (Supplementary Fig. 15). This suggests that the arrangement of Pt-complexes core ( R )-1 differed from that of Agg-A and Agg-DH. The AFM observation confirmed the single right-handed helical nanofiber of Agg-SH, which shows helical pitches of ∼100 nm and a height of 40 nm (Fig. 4 C). The changes in CD spectra of Agg-SH at 310 nm during the heating process exhibited the non-sigmoidal curve shape with T e (K), indicative of cooperative growth. The equilibrium constant for the elongation process of Agg-SH is K E2 = 7.82 x 10 6 at 308 K, and T’ e of Agg-SH is higher than T e of Agg-DH, implying that the formation of Agg-SH is thermodynamically favored com-pared with Agg-DH formation (Supplementary Figs. 16 and 17). Therefore, the formation of Agg-SH was obtained after ultrasonication treatment. In addition, the intermolecularly hydrogen-bonded Agg-DH and Agg-SH states of ( R )-1 were investigated by Fourier-transform infrared (FT-IR) spectroscopy at room temperature (Supplementary Fig. 18). For Agg-DH of Pt-complexes ( R )-1 , the intermolecular hydrogen bonding of amide groups can be characterized by the appearance of the N − H and C = O stretching frequencies in the FT-IR spectrum at 3281 and 1650 cm − 1 , respectively. In the FT-IR spectrum of Agg-SH, intermolecular hydrogen bonding of amide groups leads to a further shift of the N − H and C = O stretching frequencies at a lower wavenumber of 3244 and 1644 cm − 1 , respectively. Notably, intermolecular hydrogen bonds between amide groups for Agg-SH are found to be stronger (lower wavenumbers of the respective stretching frequencies) than intermolecular hydrogen bonds for Agg-DH. We further investigated the Agg-DH and Agg-SH (1.0 mM) by variable temperature 1 H-NMR. Upon increasing the temperature, the aromatic protons (H1, H2, H4) of terpyridine moiety in Pt-complexes core ( R )-1 shifted to a downfield in a mixture of DMSO-d 6 and D 2 O (6:4 v/v) (Supplementary Figs. 19 and 20), indicating π–π stacking between the terpyridine moiety of Agg-DH and Agg-SH, respectively. In particular, the broad signal located at 9.0 ppm, as assigned to the proton (H1) of terpyridine moiety in Agg-SH, is slightly upfield-shifted compared to that of Agg-DH. This suggests that the terpyridine moiety in Agg-SH is more tightly packed via π–π stacking interactions. Furthermore, 2D NOESY experiments of Agg-SH were conducted at 333 K. The 2D NOESY spectrum revealed close peaks between H4 and H2, H5 and H3, and H1 and H5, indicating a face-to-face arrangement of the terpyridine moiety. This suggests a strong contribution of π–π stacking interactions to the thermodynamic supramolecular packing of Agg-SH, likely resulting in a twisted face-to-face arrangement (Supplementary Fig. 21). To further extend the study on pathway complexity of ( R )-1 , the kinetic experiment was conducted at different temperatures. The transformation from Agg-A to Agg-DH occurs with helical inversion in the kinetic experiment at 308 K, indicating a higher activation barrier for the pathway of Agg-SH. Reflecting on the degree of aggregation shown in Fig. 3 , we reasoned that Agg-A is potentially able to form the Agg-SH in time evolution. This hypothesis reconstructed the energy landscape of ( R )-1 as shown in Scheme 1 , in which Agg-A becomes the on- and off-pathway intermediates for forming Agg-DH and Agg-SH, respectively. If this is the case, then metastable Agg-A can be a supramolecular assembly that has the capacity to differentiate into both single and double helical nanofiber structures. In a 200 µM solution of 1 at 308 K under pre-equilibrium, the distribution of ( R )-1 is as follows: 63 µM of monomer and 137 µM of Agg-A based on isodesmic mode. Due to the presence of the on-pathway intermediate, Agg-A is the candidate that can lead to transformation into Agg-DH. On the other hand, when the proportion between monomer and Agg-A was changed to 168 µM of monomer and 32 µM of Agg-A at 333 K under pre-equilibrium, the transformation from Agg-A into Agg-SH occurred (Fig. 4 D). Additionally, the lower the concentration of Agg-A, the shorter the lag phase, indicating that Agg-A is an off-pathway intermediate to the formation of Agg-SH. Remarkably, an intermediate of Agg-A gave rise to a different outcome depending on temperature; that is, there was a critical switch in the self-assembly pathway. Thus, the assembling condition is amplified and plays an integral role in determining the final outcome, which is reminiscent of the emergent behavior that arises from a non-equilibrium system with pathway complexity. Interestingly, Pt-complexes ( R )-1 formed three different formations: Agg-A, -DH, and -SH. Enumerating all conceivable energetic diagrams with pathway complexity, we could reveal that the present system originates from a delicate balance between the three different aggregation pathways. In other words, off- and on-pathways of Agg-A contribute to inhibiting the spontaneous polymerization of Agg-DH and Agg-SH. It is worth mentioning that this process is analogously relevant to a particular type of amyloid fibril formation: that is, nucleated polymerization with competing off- and on-pathway aggregates. After reflecting on this mechanism, we were motivated to explore the possibilities for the living supramolecular polymerization of ( R )-1 . This notion prompted us to ap-ply sonication to a solution of Agg-A. As predicted, we obtained the single helical nanofibers of Agg-SH. Seeded supramolecular polymerization. As mentioned, the metastable Agg-A was sonicated for 60 min at 283 K to produce short fragments of Agg-SH, so-called Agg-SH seed. The seeds show narrow length polydispersity (PDI, ( L w /L n ) = 1.16) with a number-average length (L n ) of 250 nm (Fig. 5 ). When Agg-A and Agg-SH seed were mixed in a 1:50, 1:100, and 1:150 ratio ([Agg-SH seed ]:[Agg-A]) at 308 K, the effective transformation of metastable Agg-A into Agg-SH was observed in CD spectra changes at 520 nm. Following the addition of Agg-SH seed to an excess amount of Agg-A, the supramolecular polymerization was initiated without a lag time and proceeded linearly with respect to the reaction time (Supplementary Fig. 22). The logarithm of the apparent polymerization rate, log(d(at 520 nm)/dt) and the amount of added Agg-SH seed were proportional with a slope of 1.05, indicating that the polymerization reaction is of first order with respect to Agg-SH seed (that is, chain-growth polymerization). In contrast, the seeding experiments using Agg-SH seed did not initiate supramolecular polymerization under identical experimental conditions applied to kinetically trapped Agg-DH. This is due to the higher kinetic stability of Agg-DH compared to Agg-A. Thus, the concentration of Agg-SH seed was increased in the ratio of [Agg-SH]/ [Agg-DH] to reduce the kinetic stability of Agg-DH. Upon increasing the proportion of seed, the transformation of Agg-DH into Agg-SH was initiated without a lag time and proceeded linearly with respect to the reaction time (Fig. 5 ). Additionally, the SEM images were taken after seeded experiments, in which the length of elongated single helical nanofibers was dependent on the ratio of Agg-SH seed , and the nanofibers were analyzed and visualized in histograms (Fig. 5 and Supplementary Fig. 23). Importantly, the length of obtained Agg-SH was proportional to the ratio of the total concentration of added Agg-SH seed to the initial concentration of Agg-DH, PDI values were ~ 1.1 for all states. The resulting helicity followed that of Agg-SH seed . All these experimental results strongly indicate the living nature of the supramolecular polymerization of ( R )-1 . These results indicate that the thermodynamic stability order is Agg-SH > Agg-DH > Agg-A. Discussion In the present study, we have demonstrated the kinetically controlled self-assembly of Pt complex ( R )-1 , which exhibits transient helical inversion, into dynamic self-assembly with single and double helix structures. By precisely controlling the interplay between helical inversion and Pt-Pt interactions, we successfully navigated the pathway complexity, involving both interfiber and inter-molecular interactions under time evolution. The chiral building unit of ( R )-1 is attributed to the transient helical inversion between P-type Agg-A and M-type Agg-A as metastable states. This contributes to the suppression of spontaneous self-assembling processes. Therefore, the unique time evolution with transient helical inversion was found in kinetic analysis. Interestingly, in time evolution for Agg-DH at lower temperatures, the resulting kinetically trapped supramolecular polymers (Agg-DH) exhibited double helical structures via interfiber interactions with Pt-Pt interactions. Furthermore, the transformation into Agg-SH at higher temperatures is revealed to induce unexpected thermodynamically favored states of single helical structures by temperature programming-related activation barriers for pathway complexity in supramolecular polymerization. Selective pathway complexity was not only regulated by seeded living supramolecular polymerization but also controlled the length and helicity of the supramolecular polymers. By elucidating the kinetic control over pathway complexity in supramolecular polymerization, we provide valuable insights that can guide the rational design and engineering of functional materials with tailored properties. Through a combination of experimental investigations and theoretical analyses, this study offers a comprehensive understanding of the pathway complexity involved in supramolecular polymerization. Methods Measurements. The 1 H and 13 C NMR spectra were taken on a Bruker DRX 300, DRX 500 and mass spectroscopy samples were analyzed on a LCQ Fleet Ion Trap Mass Spectrometer (Thermo fisher). A UV-visible spectrophotometer (Jasco V-750) was used to obtain the absorption spectra. IR spectra were observed over the range 500-4000 cm-1 with a Thermo Scientific Nicolet iS 10 instrument. The fluorescence spectra were obtained using a spectrophotometer (Jasco FP-8500). Circular Dichroism (CD) Studies. The CD spectra were recorded on a Jasco J-1500 CD spectrophotometer. The CD spectra were determined over the range of 250-800 nm using a quartz cell with 1.0 and 10.0 mm path lengths. Scans were taken at a rate of 500 nm/min with a sampling interval of 1 nm and a response time of 0.5s. Atomic Force Microscopy (AFM) Studies . AFM measurements were performed by using an XE-100 and a PPP-NCHR 10 M cantilever (Park systems). The AFM samples were prepared by spin-coating (2000 rpm) onto freshly cleaved Muscovite Mica, and images were recorded with the AFM operating in a noncontact mode in the air at RT with a resolution of 1024 × 1024 pixels, using moderate scan rates (0.3 Hz) and analyzed using XEI software developed by Park systems. SEM observation . FE-SEM images were observed using a Tescan (S8000). The images of samples using an accelerating voltage of 10 kV and an emission current of 8 μA. Samples were prepared by dropping solutions of supramolecular nanostructure on glasses, followed by spinning, drying, and coating them with a thin layer of Pt to increase the contrast. Calculation of Avtivation Energy CD = CD 0 + (Plateau-CD 0 )*(1-exp (-k inv *t)) Where the value of CD 0 is the initial CD signal when time is zero, and Plateau is the CD value at infinite time. This equation is the result of considering the whole inversion process. In this way, the first step follows a pseudo-first-order kinetics where the k inv can be obtained representing the ln(CD/CD 0 ) vs. time for each temperature in the shortest times where the evolution of the CD follows a first-order kinetic process. [52, 53] After this, k inv is the double assuming that both helices have the same energy. R value used is 8.314 J·K −1 ·mol −1 , k B = 1.381 × 10 −23 J·K −1 and h = 6.626 × 10 −34 J·s −1 . Preparation of Self-Assembled Samples. The stock solution of monomeric ( R )-1 was prepared in dimethyl sulfoxide (DMSO). The monomeric solution was then injected into the required volume of H2O to adjust the final concentration of the required choice. The final solvent mixture ratio of DMSO and H 2 O was 6:4 (v/v). Preparation of seeds. The seeds were prepared by applying sonication to aqueous solution of Agg-A at 10 °C. The Agg-SH seed was obtained via sonication at 10 °C for 1 hr (3 ml, 200 µM). By applying sonication, the Suparmolecular polymers fragmented into short pieces with relatively narrow length distribution were obtained, which was confirmed through analysis of SEM images, as shown in Fig.5 and Supplementary Fig.23 Declarations Acknowledgments This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIT) (Grant No. 2021R1A2C2007664, 2022R1A4A1022252, and RS-2023-00241926). This research was supported by Korea Basic Science Institute(National research Facilities and Equipment Center) grand funded by Ministry of Science and ICT.(No.RS-2024-00402475) Author contribution J. H. Jung. and S. H. Jung conceived the idea for this project. H. M. Han. and M. J. Kim. performed the experiments, analyzed the data, and produced the artwork under the direction of J. H. Jung. and S. H. Jung. All authors contributed to the manuscript. Competing interests The authors declare no competing interests. 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Elucidation of the key role of Pt···Pt interactions in the directional self-assembly of platinum(II) complexes. Proc. Natl Acad. Sci. USA 119 , e2200365119 (2022). Li, B. et al. Supramolecular assembly of organoplatinum(II) complexes for subcellular distribution and cell viability monitoring with differentiated imaging. Angew. Chem. Int. Ed. 61 , e202209209 (2022). Kim, K. Y. et al. Co-assembled supramolecular nanostructure of platinum(II) complex through helical ribbon to helical tubes with helical inversion. Angew. Chem. 131 , 11835–11840 (2019). Wan, Q. et al. Counteranion- and solvent-mediated chirality transfer in the supramolecular polymerization of luminescent platinum(II) complexes. Angew. Chem. 130 , 17435–17439 (2018). Ogi, S. et al. Living supramolecular polymerization realized through a biomimetic approach. Nat. Chem. 6 , 188–195 (2014). Smulders, M. M. J. et al. How to distinguish isodesmic from cooperative supramolecular polymerisation. Chem. Eur. J. 16 , 362–367 (2010). De Greef, T. F. A. et al. Supramolecular polymerization. Chem. Rev. 109 , 5687–5754 (2009). Scheme Scheme 1 is available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files SINat.Comm.docx Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions scheme1.png Scheme 1. Chemical structures of Pt-complexes and pathway complexity in supramolecular polymerization. (A) Chemical structures of terpyridine-based Pt-complex ( R )-1. (B) Competitive aggregation pathways of ( R )-1. (C) Schematic representation of the energy landscape of assemblies ( R )-1 with different temperatures at 308 K (left) and 333 K (right). Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6654028","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":459719529,"identity":"1845d82c-bd34-4983-8725-e0b3a8c60fcb","order_by":0,"name":"Sung Ho Jung","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAx0lEQVRIiWNgGAWjYDACCYYEIGkD4yYQrSWNNC0gcJgELfKzG55JF/w6b7ddIoHxww+GtHyCWgzuHEiTntl3O3nnjARmyR6GHMsGglokEtKkeXtuJxvcSGCQZmCoMCDssBlgLedAWph/E6WF4QZQC8+PA3ZALWxAW3IIawGqTLbmbUhOMDjzsM2yxyCNGIflJN7m+WNnb3A8+fCNHxXJRDiMgSeBgbGNIbGBgbEBaCkRGhgY2A8wMPxhsCdK7SgYBaNgFIxMAACgpzp/P9iTMQAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0002-5585-1086","institution":"Gyeongsang National University","correspondingAuthor":true,"prefix":"","firstName":"Sung","middleName":"Ho","lastName":"Jung","suffix":""},{"id":459719530,"identity":"bdd6ff35-0b84-43b9-b3c6-16bd67b616db","order_by":1,"name":"Hyeon Min Han","email":"","orcid":"","institution":"Gyeongsang National University","correspondingAuthor":false,"prefix":"","firstName":"Hyeon","middleName":"Min","lastName":"Han","suffix":""},{"id":459719531,"identity":"a2c8a792-a3af-4d07-941c-a30aac5f7806","order_by":2,"name":"Min Joo Kim","email":"","orcid":"","institution":"Gyeongsang National University","correspondingAuthor":false,"prefix":"","firstName":"Min","middleName":"Joo","lastName":"Kim","suffix":""},{"id":459719532,"identity":"999782d4-aea5-46a7-804b-bc597aad0c3b","order_by":3,"name":"Jong Hwa Jung","email":"","orcid":"","institution":"Gyeongsang National University","correspondingAuthor":false,"prefix":"","firstName":"Jong","middleName":"Hwa","lastName":"Jung","suffix":""}],"badges":[],"createdAt":"2025-05-13 09:46:46","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6654028/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6654028/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":83359549,"identity":"9f45aa12-c000-49f8-9b4b-a1bc40c6e323","added_by":"auto","created_at":"2025-05-23 16:08:39","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":124461,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTransient helical inversion with transformation kinetics. (A)\u003c/strong\u003e Concentration-dependent CD spectra changes of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1 \u003c/strong\u003ein DMSO and H\u003csub\u003e \u003c/sub\u003eO (6:4 v/v) at 293 K. (\u003cstrong\u003eB)\u003c/strong\u003e Plot of initial CD intensity at 293 nm versus concentrations of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1\u003c/strong\u003e at 293 K. (\u003cstrong\u003eC)\u003c/strong\u003e Arrhenius plot of the helical inversion rate obtained by variable temperature global fitting procedure. (\u003cstrong\u003eD)\u003c/strong\u003e Schematic representation of helical inversion. (\u003cstrong\u003eE)\u003c/strong\u003e Time-dependent CD spectra changes of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1\u003c/strong\u003e (c\u003csub\u003eT\u003c/sub\u003e = 200 μM) in DMSO and H\u003csub\u003e2\u003c/sub\u003eO (6:4 v/v) at 308 K. (\u003cstrong\u003eF)\u003c/strong\u003e Zoom in for the MMLCT region in panel €. (\u003cstrong\u003eG)\u003c/strong\u003e Concentration-dependent kinetics of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1\u003c/strong\u003e at 308 K. \u003cstrong\u003eH\u003c/strong\u003e Time at which 50% of final CD intensity versus concentrations of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1\u003c/strong\u003e at 308 K.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/70b7b22df6f009502e2049bc.png"},{"id":83359550,"identity":"a6aa4549-f79e-49a4-9d14-03097b9117f7","added_by":"auto","created_at":"2025-05-23 16:08:39","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":126105,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMorphological evolution from single into double helix. (A-D) \u003c/strong\u003eTime-dependent SEM images in the transformation of Agg-A into Agg-DH at (\u003cstrong\u003eA\u003c/strong\u003e)1h, (B)5h, (\u003cstrong\u003eC\u003c/strong\u003e)10h, and (D) 19h. (\u003cstrong\u003eE\u003c/strong\u003e) AFM image of Agg-DH. (\u003cstrong\u003eF\u003c/strong\u003e) PL spectra of Agg-A and Agg-DH (200 μM)\u003cem\u003e \u003c/em\u003ein DMSO and H\u003csub\u003e2\u003c/sub\u003eO (6:4 v/v) at 298 K.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/c261ca7b2029971e9bf3fabf.png"},{"id":83359887,"identity":"45fb36c5-e992-4c27-a7a8-555c5e907213","added_by":"auto","created_at":"2025-05-23 16:16:39","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":43241,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDifferentiating the mechanism of supramolecular self-assembly. (A)\u003c/strong\u003e CD spectra of Agg-A (200 μM) and Agg-DH (200 μM) in DMSO and H\u003csub\u003e2\u003c/sub\u003eO (6:4 v/v) at 293 K. (\u003cstrong\u003eB)\u003c/strong\u003e Degree of aggregation of Agg-A and Agg-DH as a function of temperature, fitted to the isodesmic and cooperative model.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/6dbb0c080704199144ccb3e9.png"},{"id":83359554,"identity":"aab5f3b8-d252-4953-819d-3e82aa99af1f","added_by":"auto","created_at":"2025-05-23 16:08:39","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":96085,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eKinetic and thermodynamic studies of the supramolecular self-assembly of single and double helices. (A) \u003c/strong\u003eCD spectra of Agg-DH (200 μM) and Agg-SH (200 μM) in DMSO and H\u003csub\u003e2\u003c/sub\u003eO (6:4 v/v) at 293 K. (\u003cstrong\u003eB)\u003c/strong\u003e Degree of aggregation of Agg-DH and Agg-SH as a function of temperature, fitted to the cooperative model. (\u003cstrong\u003eC)\u003c/strong\u003e AFM image of Agg-SH. (\u003cstrong\u003eD)\u003c/strong\u003e Kinetics of Agg-A into Agg-SH (150 and 200 μM) at 333 K. The insert to (\u003cstrong\u003eD)\u003c/strong\u003e shows the time at which 50% of the final CD intensity versus concentrations of \u003cstrong\u003e(\u003c/strong\u003e\u003cem\u003e\u003cstrong\u003eR\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e)-1.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/1daa6e2bdedecb6ce5f20a0d.png"},{"id":83359556,"identity":"8d36b65e-52d1-49b1-806c-782d89484eed","added_by":"auto","created_at":"2025-05-23 16:08:39","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":281632,"visible":true,"origin":"","legend":"\u003cp\u003eSeeded living supramolecular polymerization. (A) Time course of the degree of aggregation after the addition of Agg-SH\u003csub\u003eseed\u003c/sub\u003e to Agg-DH at 308 K. (B) Log-log plot of the decrease rate at 520 nm (s\u003csup\u003e-1\u003c/sup\u003e) as a function of seed concentration (M), showing a linear relationship with a slope of 1.05. (C) Cumulative histogram of the length distributions of the seed and supramolecular polymers. (D) Plots of the number-averaged length (L\u003csub\u003en\u003c/sub\u003e), weight-averaged length (L\u003csub\u003ew\u003c/sub\u003e), and PDI (L\u003csub\u003ew\u003c/sub\u003e/L\u003csub\u003en\u003c/sub\u003e) of the seed and supramolecular polymers. (E-H) SEM images of supramolecular polymers obtained through seeded supramolecular polymerization (ratio of [Agg-SH\u003csub\u003eseed\u003c/sub\u003e]:[Agg-DH]; (E) seed, (F) 1:1, (G) 1:2, and (H) 1:3) (ca. 100 fibers traced in each case).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/267a7c98720d4c5b3f467a06.png"},{"id":100373642,"identity":"78d46906-8daf-4605-bdbc-366358146174","added_by":"auto","created_at":"2026-01-16 08:15:50","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1646844,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/ac7e1527-c644-4a7f-a819-6745414661cc.pdf"},{"id":83359569,"identity":"15dd7630-dc7e-430f-8a09-38b38e3fba7e","added_by":"auto","created_at":"2025-05-23 16:08:39","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":3781702,"visible":true,"origin":"","legend":"Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions","description":"","filename":"SINat.Comm.docx","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/4113d3e5ce93ca135215407f.docx"},{"id":83360401,"identity":"d0980f47-0f67-4aac-8799-5521b24bfc07","added_by":"auto","created_at":"2025-05-23 16:24:39","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":265593,"visible":true,"origin":"","legend":"\u003cp\u003eScheme 1. Chemical structures of Pt-complexes and pathway complexity in supramolecular polymerization. (A) Chemical structures of terpyridine-based Pt-complex (\u003cem\u003eR\u003c/em\u003e)-1. (B) Competitive aggregation pathways of (\u003cem\u003eR\u003c/em\u003e)-1. (C) Schematic representation of the energy landscape of assemblies (\u003cem\u003eR\u003c/em\u003e)-1 with different temperatures at 308 K (left) and 333 K (right).\u003c/p\u003e","description":"","filename":"scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-6654028/v1/a9fd40c4ab479f66fed4e5d9.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions","fulltext":[{"header":"Introduction","content":"\u003cp\u003eSupramolecular polymers, formed by non-covalent interactions between monomeric units through spontaneous self-assembly processes, have emerged as a captivating area of research due to their potential applications in fabricating advanced soft materials with unique properties.\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e Elucidating these fundamental aspects holds immense promise for the directed design of supramolecular materials with tailored functionalities.\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e,\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e The supramolecular stacking arrangements significantly impact their material properties as exhibited in solution or bulk states, influencing phenomena such as gel formation and protein aggregation.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e,\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e For instance, a comprehensive understanding of disorders linked to protein aggregation from proteins converting into their amyloid forms, such as Alzheimer\u0026rsquo;s and Parkinson\u0026rsquo;s diseases, is a fundamental prerequisite for deciphering the pathway complexity involved in aggregation networks.\u003csup\u003e\u003cspan additionalcitationids=\"CR11\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e Therefore, programming the organization of supramolecular systems through high-precision self-assembly along diverse pathways is a key strategy for optimizing functional properties. However, achieving this level of control remains a challenging requirement in the field.\u003c/p\u003e \u003cp\u003eBy understanding the well-established mechanisms of supramolecular polymerization in recent years, such as isodesmic or cooperative models, remarkable control over supramolecular polymerization was achieved by gaining deep insights into the thermodynamics and kinetics of these processes.\u003csup\u003e\u003cspan additionalcitationids=\"CR14\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e Since the report by Meijer and coworkers on pathway complexity of π -conjugated SOPV in supramolecular polymerization, on- and off-pathway intermediates with helical inversion were proved by kinetic analysis.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e Such supramolecular interactions in these materials are dynamic, allowing a single monomeric molecule to follow diverse pathways in multiple aggregation processes. These materials can be engineered to exhibit sensitivity to the chemical reaction and respond to a chiral environment.\u003csup\u003e\u003cspan additionalcitationids=\"CR18 CR19 CR20 CR21 CR22 CR23\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e Understanding the kinetics of the pathway complexity is crucial, as it governs the self-assembly processes. Pathway complexity in supramolecular polymers serves as a powerful benchmark for mimicking the natural processes of biomolecules, facilitating the creation of intricate, functional structures.\u003csup\u003e\u003cspan additionalcitationids=\"CR26 CR27\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e Despite its significance, the kinetics of chirality evolution in natural systems remains poorly understood, continuing to captivate researchers from various disciplines. Unraveling these kinetic processes is essential for advancing the field of supramolecular polymerization and its applications in creating sophisticated materials.\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eTo date, rational strategies for control over pathways in self-assembly have primarily relied on molecular design, competition between inter and intramolecular hydrogen bonding, dynamic covalent bonds, and the self-assembling protocol.\u003csup\u003e\u003cspan additionalcitationids=\"CR32 CR33 CR34 CR35 CR36 CR37 CR38 CR39\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e However, exploiting pathway complexity driven by helical inversion with metal-metal interaction to tune self-assembly processes in time evolution is rare and considerably more challenging. We are particularly interested in the self-assembly of Pt complexes, a class of chromophores that is of interest for ap-plications owing to their outstanding photophysical prop-erties.\u003csup\u003e\u003cspan additionalcitationids=\"CR42\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e In our earlier work, we showed dynamic self-assembling behavior with helical inversion and circularly polarized luminescence (CPL).\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e Although the photophysical properties and self-assembly behaviors of supramolecular polymers derived from Pt(II) complexes have been extensively studied by our group\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e and others,\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e,\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e the selective pathways and transient helical inversions occurring during supramolecular polymerization have not yet been investigated.\u003c/p\u003e \u003cp\u003eBy introducing steric effects of the biphenyl group and alkyl chain in molecular design, we achieved the revealing of the self-assembling pathways of the Pt complex in supramolecular polymerization with unique time evolution. Herein, we have presented the kinetically controlled self-assembly of Pt complex \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e or \u003cb\u003eS\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e into the single and double helix structures via transient helical inversion in supramolecular polymerization with time evolution, which unprecedented kinetic behavior (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The detailed helical inversion in selective pathway dynamics, along with its unique time evolution, was investigated using circular dichroism (CD) spectroscopy. The activation energy for the transient helical inversion from \u003cem\u003eM\u003c/em\u003e-type to \u003cem\u003eP\u003c/em\u003e-type aggregates in the metastable state was determined through temperature-dependent CD observations. Distinct morphological differences between kinetically trapped aggregates and thermodynamic aggregates were observed through scanning electron microscopy (SEM) and atomic force microscopy (AFM). Although the time-dependent evolution appeared complex, we successfully demonstrated the pathway complexity of controllable aggregation pathways through temperature programming. Thermodynamic studies were conducted to evaluate the stability of both kinetic and thermodynamic aggregates. Furthermore, seeded living supramolecular polymerization was utilized to control selective pathway dynamics.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e \u003cb\u003eMolecular design and synthesis.\u003c/b\u003e In this study, terpyridine-based Pt(II) complexes \u003cb\u003e1\u003c/b\u003e possessing \u003cem\u003eR\u003c/em\u003e- or \u003cem\u003eS\u003c/em\u003e-enantiomeric alanine moiety were designed with unsaturated fatty acid containing a chiral amide group at one terminus and a biphenyl group and alkyl chain at the other. The molecular design derived from a previously reported monomer (chloroplatinum (II) complex) (Supplementary Scheme 1), known to form helical supramolecular tubes as a consequence of enhanced chiroptical properties, including circularly polarized luminescence generated through a unique dynamic morphological transformation and helical inversion. In this study, we focused on modulating π - π and Pt-Pt interactions in supramolecular polymerization by introducing an alkyne ligand. Specifically, substituents were incorporated to investigate the dynamic self-assembly process in supramolecular polymerization, which has been extensively studied for its tunable optical and electronic properties.\u003csup\u003e\u003cspan additionalcitationids=\"CR46\" citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e Thus, the previously reported chloroplatinum (II) complex was coordinated with alkynyl ligands, such as the biphenyl group and alkyl chain, and we obtained the structures of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e. Complexes (\u003cb\u003eR\u003c/b\u003e and \u003cb\u003eS\u003c/b\u003e)\u003cb\u003e-1\u003c/b\u003e were synthesized according to synthetic pathways, as shown in Scheme S1 in the supporting information. All the complexes have been characterized by \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH and \u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003eC NMR, FT-IR, elemental analysis, and HS-ESI mass spectrometry.\u003c/p\u003e \u003cp\u003e \u003cb\u003eAggregation pathway from Agg-A to Agg-DH with helical inversion.\u003c/b\u003e The supramolecular polymerization was demonstrated through their aggregation pathway in a mixture of dimethyl sulfoxide (DMSO) and water. In this system, the complex \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e was molecularly dissolved in DMSO at 293K, allowing us to study the dynamic self-assembly process across a broader range of concentrations using a solvent mixing protocol with water. Initially, the self-assembling behavior of complexes \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e in a mixture of DMSO and water was investigated by circular dichroism (CD) and UV-Vis spectroscopy. Notably, when a DMSO solution of monomeric \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e was rapidly injected into the water, we could observe the concentration-dependent helical inversion of aggregated \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e (in the following denoted Agg-A) (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The final solvent of DMSO: water ratio was 6:4, and the resulting \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e concentrations ranged between 125 \u0026micro;M and 400 \u0026micro;M. Upon increasing the concentration of Agg-A at 293K, the nega-tive Cotton CD signal at 293 nm increased up to 200 \u0026micro;M, while the corresponding positive Cotton CD signal in-creased at 400 \u0026micro;M, which strongly indicated that helical inversion of Agg-A from P-type (right-helicity) to M-type (left-helicity) occurs depending on the concentration of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e, as evidenced by the mirror-image of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eS\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e with Cotton effect (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Fig.\u0026nbsp;1). In the UV-Vis spectra of Agg-A in a mixture of DMSO and water (6:4, v/v), the high-energy absorption band in 270\u0026ndash;350 nm decreased, while a lower-energy band in the 370\u0026ndash;500 nm range, assignable to metal-to-ligand charge transfer (MLCT), redshifted to around 470 nm. These observations imply that the intermolecular interactions in assembled Agg-A were mainly assisted by π-π interactions (Supplementary Fig.\u0026nbsp;2).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further characterize the Agg-A with helical inversion, atomic force microscopy (AFM) analysis was performed. When this solution was spin-coated onto a mica substrate, AFM observation revealed the helical nanofibers (Supplementary Fig.\u0026nbsp;3). The height of Agg-A in M-type and P-type assemblies was \u0026asymp;\u0026thinsp;12 nm. The right-handed P-type and left-handed M-type helical nanofibers co-existed, respectively. The ratio of right- and left-handed nanofibers depended on the concentration of Agg-A and was consistent with the Cotton effect observed in CD spectra (Supplementary Fig.\u0026nbsp;3).\u003c/p\u003e \u003cp\u003eInterestingly, the CD spectrum of Agg-A composed of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e (200 \u0026micro;M) in a mixture of DMSO and water (6:4, v/v) after aging for 1 day showed a significantly different spectral signature with a further increase in the negative CD signal at λ\u003csub\u003emax\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;320 nm. Additionally, a weak positive first Cotton effect at 567 nm and a weak negative second Cotton effect at 482 nm corresponding to metal-metal-to-ligand charge transfer (MMLCT) was observed, as characterized by the appearance of an absorption shoulder band at 540 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eF and Supplementary Fig.\u0026nbsp;2).\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e These observations suggest that metastable Agg-A of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e transformed into thermodynamically favored aggregates (in the following denoted Agg-DH) via dynamic intermolecular interactions, particularly with enhanced Pt-Pt interaction during supramolecular polymerization.\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e The time-dependent transformation with sigmoidal growth of helical supramolecular polymers (Agg-DH) suggests the possible existence of competing pathways in the self-assembly of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e.\u003c/p\u003e \u003cp\u003eTo get a deeper understanding of the aggregation pathway with a characteristic of the lag phase, kinetic experiments were carried out to evaluate the relationship between helical inversion and concentrations of Agg-A (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Fig.\u0026nbsp;4). The unique kinetic profiles were observed in the time evolution accompanying the helical inversion of Agg-A, where the resulting kinetic profiles exhibit a sigmoidal growth pattern with a lag phase characteristic of the presence of a metastable state in the supramolecular polymerization, indicating autocatalysis processes.\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e A plot of half-time, t\u003csub\u003e50\u003c/sub\u003e (time at which 50% of the aggregation process) against concentrations, obtained from corresponding time-dependent CD spectra changes, versus corresponding concentration of Agg-A gives V-shaped kinetic profiles with a decrease in the t\u003csub\u003e50\u003c/sub\u003e with closing at 200 \u0026micro;M (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eH). At higher concentrations (400 \u0026micro;M), a positive CD signal appeared at 293 nm in the initial stages of the assembly process and then transformed into a negative CD signal (λ\u003csub\u003emax\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;320 nm) at later times, suggesting the initial formation of M-type Agg-A as an off-pathway intermediate that then converted into thermodynamically favorable P-type Agg-A as an on-pathway intermediate during time-evolution toward Agg-DH (Supplementary Fig.\u0026nbsp;5). Note-worthy is that the t\u003csub\u003e50\u003c/sub\u003e is longer at 400 \u0026micro;M than at 200 \u0026micro;M (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eF). In contrast, the presence of a more extended lag phase in kinetic profiles at the lowest concentrations (below 200 \u0026micro;M) and an inverted dependence of t\u003csub\u003e50\u003c/sub\u003e on concentration was observed in kinetic studies (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eH). This is attributed to the dilution effect, leading to the dissociation process of P-type Agg-A in equilibria between monomer and Agg-A. This concentration dependence indicates that M-type Agg-A is an off-pathway aggregate, and P-type Agg-A is an on-pathway aggregate in transformation for Agg-DH. In conclusion, the supramolecular polymerization of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e exhibited a kinetic pathway with helical inversion, as evident from the changes in CD intensity at 320 nm. To clearly investigate the influence of helical inversion from metastable M-type Agg-A to stable P-type Agg-A, changes in CD signal (400 \u0026micro;M, at 345 nm) were monitored as a function of time at different temperatures. The activation energy for helical inversion from M-type to P-type Agg-A was estimated to be 167 kJmol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using an Arrhenius plot (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Fig.\u0026nbsp;6). This value is sufficient to suppress the helical inversion at 293 K. Additionally, based on the Eyring plot, activation enthalpy (ΔH\u003csup\u003e\u0026ne;\u003c/sup\u003e) and entropy (ΔS\u003csup\u003e\u0026ne;\u003c/sup\u003e) for helical inversion were 164 kcal mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 218 Jmol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eK\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively (Supplementary Fig.\u0026nbsp;6). These results indicate that the transient helical inversion of metastable Agg-A contributes to unique time evolution with a lag phase in the transformation into the thermodynamically favored state Agg-DH compared with Agg-A. Therefore, conformational kinetic structures in a transient helical inversion of Agg-A play a critical role in modulating the kinetic pathway in supramolecular polymerization.\u003c/p\u003e \u003cp\u003e \u003cb\u003eMorphological transformation from single fiber to double helix.\u003c/b\u003e To further investigate the influence of transient helical inversion with unique kinetic profiles on the morphology of the self-assembling characteristics of Agg-A and Agg-DH, we conducted time-dependent scanning electron microscopy (SEM) and atomic force microscopy (AFM). Combined time evolution experiments, along with SEM and AFM imaging using the same solutions, were used to visualize the transformation of Agg-A into Agg-DH at 200 \u0026micro;M. In the lag phage, the metastable Agg-A is characterized by the formation of thin nanofibers of isolated aggregates with a uniform height of 12 nm (Supplementary Fig.\u0026nbsp;2). Completely discrete double-helix structures were observed by AFM and SEM when the solution of completely transformed Agg-DH. As seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, these interacting fibers are intertwined to form right-handed double-helix structures with helical pitches of \u0026sim;180 nm and a height of 60 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eE). Furthermore, the induction of positive first Cotton CD signals at 570 nm in the region of MMLCT transition of Agg-DH is rationalized by the presence of Pt-Pt interactions of Pt complexes core, inducing intertwined helical arrangement of Pt complexes core of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e in the rotational displacement upon transformation (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). We suggest that the right-handed P-type Agg-A further merge to form right-handed double-helix structures (Agg-DH) via interfiber interaction with Pt-Pt interaction.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo understand the reasons underlying unique time evolution with morphological transformation, the MMLCT excited state of Agg-DH was confirmed by the emission spectrum and wide-angle X-ray diffraction (WXRD). In emissive properties, time-dependent PL measurements for \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e were observed in the same solvent system. Initially, the PL spectrum of Agg-A shows a very weak signal at 695 nm, which increases gradually with aging times (Supplementary Fig.\u0026nbsp;7). The enhancement of the PL intensity is mainly due to the enhanced Pt\u0026ndash;Pt interactions upon the formation of Agg-DH. Additionally, Agg-DH aggregate was studied using wide-angle X-ray diffraction (WXRD). A characteristic Pt-Pt interaction peak at q\u0026thinsp;=\u0026thinsp;18.7 nm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with a spacing of 0.34 \u0026Aring; was observed (Supplementary Fig.\u0026nbsp;8). These findings reveal that fibers interact with neighboring fibers, thus supporting the hypothesis that the core of Pt-complex \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e remains on the fibers\u0026rsquo; surface and, together with substituent flexibility, determines higher-order structure formation. These results demonstrate that \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e undergoes a unique time evolution with pathway complexity, including the morphological transformation from fiber to double-helix structures via interfiber interaction with Pt-Pt interaction.\u003c/p\u003e \u003cp\u003e \u003cb\u003eMechanism of supramolecular polymerization and thermodynamic parameters.\u003c/b\u003e Temperature-dependent CD and UV-Vis spectroscopy were performed to gain further insight into the supramolecular mechanism. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, Agg-A and Agg-DH exhibited clearly distinguishable heating curves. The data from several temperature-dependent CD intensity or UV-Vis absorption changes from 293 to 373 K in DMSO/water (6:4, v/v) at different total concentrations ranging from 100 \u0026micro;M to 250 \u0026micro;M could be fitted with the isodesmic or cooperative model (Supplementary Figs.\u0026nbsp;9\u0026ndash;12).\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe sigmoidal heating curve of Agg-A indicated the metastable Agg-A following an isodesmic growth. In contrast, the Agg-DH exhibited a non-sigmodal heating curve with \u003cem\u003eT\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e (343.5 K), indicating cooperative growth. Through van\u0026rsquo;t Hoff analysis, the standard enthalpy change (Δ\u003csub\u003eAgg\u0026minus;A\u003c/sub\u003e \u003cem\u003eH\u003c/em\u003e\u0026deg;) and standard entropy change (Δ\u003csub\u003eAgg\u0026minus;A\u003c/sub\u003e \u003cem\u003eS\u003c/em\u003e\u0026deg;) for Agg-A were estimated to be -65 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and \u0026minus;\u0026thinsp;138 J mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eK\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively (Supplementary Fig.\u0026nbsp;10). Additionally, based on a van\u0026rsquo;t Hoff plot for the elongation process of Agg-DH, the standard enthalpy change (Δ\u003csub\u003eAgg\u0026minus;DH\u003c/sub\u003e \u003cem\u003eH\u003c/em\u003e\u0026deg;) and standard entropy change (Δ\u003csub\u003eAgg\u0026minus;DH\u003c/sub\u003e \u003cem\u003eS\u003c/em\u003e\u0026deg;) for Agg-DH were estimated to be -77 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and \u0026minus;\u0026thinsp;153 J mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eK\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively (Supplementary Fig.\u0026nbsp;12). The more negative standard entropy (ΔS\u0026deg;) of Agg-DH compared to Agg-A suggests that the formation of more organized double-helix structures from single-helix structures via inter-fiber interactions, along with enhanced Pt-Pt interactions, contributes to this increased negative value. As a result, the aggregation of Agg-A and Agg-DH occurs with equilibrium constants of \u003cem\u003eK\u003c/em\u003e\u003csub\u003eI\u003c/sub\u003e=7.0\u0026times;10\u003csup\u003e3\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and \u003cem\u003eK\u003c/em\u003e\u003csub\u003eE\u003c/sub\u003e=1.0\u0026times;10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 308 K, respectively, according to the corresponding propagation models. We realize that Agg-DH, with a larger \u003cem\u003eK\u003c/em\u003e\u003csub\u003eE\u003c/sub\u003e, is the thermodynamic product compared to Agg-A. These results also support that metastable Agg-A eventually transformed into the thermodynamically favored formation of Agg-DH. Additionally, the solution of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e was prepared in a mixture of DMSO and water by the cooling process, and no suitable data could be obtained due to a precipitate of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e, which resulted in undesired formation during cooling measurements. Consequently, the desired data were obtained through the heating process.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSelective pathway under non-equilibrium state.\u003c/b\u003e After ultrasonication treatment of metastable Agg-A, the unexpected formation of aggregates (in the following denoted Agg-SH) was obtained, differing from the characteristics observed for Agg-DH in CD and absorption observation (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e and Supplementary Fig.\u0026nbsp;13). The CD spectrum of Agg-SH in a mixture of DMSO and water (6:4, v/v) showed an increase in the negative CD signal at λ\u003csub\u003emax\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;310 nm and a weak positive CD signal at 540 nm corresponding to metal-metal-to-ligand charge transfer (MMLCT), in which a characteristic Pt-Pt interaction peak at q\u0026thinsp;=\u0026thinsp;18.7 nm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with a spacing of 0.34 \u0026Aring; was observed using wide-angle X-ray diffraction (WXRD). (Supplementary Fig.\u0026nbsp;14). Furthermore, the PL spectrum of Agg-SH revealed an enhanced intensity at 695 nm compared to Agg-A and Agg-DH (Supplementary Fig.\u0026nbsp;15). This suggests that the arrangement of Pt-complexes core \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e differed from that of Agg-A and Agg-DH. The AFM observation confirmed the single right-handed helical nanofiber of Agg-SH, which shows helical pitches of \u0026sim;100 nm and a height of 40 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eC). The changes in CD spectra of Agg-SH at 310 nm during the heating process exhibited the non-sigmoidal curve shape with \u003cem\u003eT\u003c/em\u003e\u003csub\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sub\u003e (K), indicative of cooperative growth. The equilibrium constant for the elongation process of Agg-SH is \u003cem\u003eK\u003c/em\u003e\u003csub\u003eE2\u003c/sub\u003e = 7.82 x 10\u003csup\u003e6\u003c/sup\u003e at 308 K, and \u003cem\u003eT\u0026rsquo;\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e of Agg-SH is higher than \u003cem\u003eT\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e of Agg-DH, implying that the formation of Agg-SH is thermodynamically favored com-pared with Agg-DH formation (Supplementary Figs.\u0026nbsp;16 and 17). Therefore, the formation of Agg-SH was obtained after ultrasonication treatment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn addition, the intermolecularly hydrogen-bonded Agg-DH and Agg-SH states of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e were investigated by Fourier-transform infrared (FT-IR) spectroscopy at room temperature (Supplementary Fig.\u0026nbsp;18). For Agg-DH of Pt-complexes \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e, the intermolecular hydrogen bonding of amide groups can be characterized by the appearance of the N\u0026thinsp;\u0026minus;\u0026thinsp;H and C\u0026thinsp;=\u0026thinsp;O stretching frequencies in the FT-IR spectrum at 3281 and 1650 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. In the FT-IR spectrum of Agg-SH, intermolecular hydrogen bonding of amide groups leads to a further shift of the N\u0026thinsp;\u0026minus;\u0026thinsp;H and C\u0026thinsp;=\u0026thinsp;O stretching frequencies at a lower wavenumber of 3244 and 1644 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. Notably, intermolecular hydrogen bonds between amide groups for Agg-SH are found to be stronger (lower wavenumbers of the respective stretching frequencies) than intermolecular hydrogen bonds for Agg-DH. We further investigated the Agg-DH and Agg-SH (1.0 mM) by variable temperature \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH-NMR. Upon increasing the temperature, the aromatic protons (H1, H2, H4) of terpyridine moiety in Pt-complexes core \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e shifted to a downfield in a mixture of DMSO-d\u003csub\u003e6\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003eO (6:4 v/v) (Supplementary Figs.\u0026nbsp;19 and 20), indicating π\u0026ndash;π stacking between the terpyridine moiety of Agg-DH and Agg-SH, respectively. In particular, the broad signal located at 9.0 ppm, as assigned to the proton (H1) of terpyridine moiety in Agg-SH, is slightly upfield-shifted compared to that of Agg-DH. This suggests that the terpyridine moiety in Agg-SH is more tightly packed via π\u0026ndash;π stacking interactions. Furthermore, 2D NOESY experiments of Agg-SH were conducted at 333 K. The 2D NOESY spectrum revealed close peaks between H4 and H2, H5 and H3, and H1 and H5, indicating a face-to-face arrangement of the terpyridine moiety. This suggests a strong contribution of π\u0026ndash;π stacking interactions to the thermodynamic supramolecular packing of Agg-SH, likely resulting in a twisted face-to-face arrangement (Supplementary Fig.\u0026nbsp;21).\u003c/p\u003e \u003cp\u003eTo further extend the study on pathway complexity of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e, the kinetic experiment was conducted at different temperatures. The transformation from Agg-A to Agg-DH occurs with helical inversion in the kinetic experiment at 308 K, indicating a higher activation barrier for the pathway of Agg-SH. Reflecting on the degree of aggregation shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, we reasoned that Agg-A is potentially able to form the Agg-SH in time evolution. This hypothesis reconstructed the energy landscape of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e as shown in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, in which Agg-A becomes the on- and off-pathway intermediates for forming Agg-DH and Agg-SH, respectively. If this is the case, then metastable Agg-A can be a supramolecular assembly that has the capacity to differentiate into both single and double helical nanofiber structures. In a 200 \u0026micro;M solution of 1 at 308 K under pre-equilibrium, the distribution of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e is as follows: 63 \u0026micro;M of monomer and 137 \u0026micro;M of Agg-A based on isodesmic mode. Due to the presence of the on-pathway intermediate, Agg-A is the candidate that can lead to transformation into Agg-DH. On the other hand, when the proportion between monomer and Agg-A was changed to 168 \u0026micro;M of monomer and 32 \u0026micro;M of Agg-A at 333 K under pre-equilibrium, the transformation from Agg-A into Agg-SH occurred (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eD). Additionally, the lower the concentration of Agg-A, the shorter the lag phase, indicating that Agg-A is an off-pathway intermediate to the formation of Agg-SH. Remarkably, an intermediate of Agg-A gave rise to a different outcome depending on temperature; that is, there was a critical switch in the self-assembly pathway. Thus, the assembling condition is amplified and plays an integral role in determining the final outcome, which is reminiscent of the emergent behavior that arises from a non-equilibrium system with pathway complexity. Interestingly, Pt-complexes \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e formed three different formations: Agg-A, -DH, and -SH. Enumerating all conceivable energetic diagrams with pathway complexity, we could reveal that the present system originates from a delicate balance between the three different aggregation pathways. In other words, off- and on-pathways of Agg-A contribute to inhibiting the spontaneous polymerization of Agg-DH and Agg-SH. It is worth mentioning that this process is analogously relevant to a particular type of amyloid fibril formation: that is, nucleated polymerization with competing off- and on-pathway aggregates. After reflecting on this mechanism, we were motivated to explore the possibilities for the living supramolecular polymerization of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e. This notion prompted us to ap-ply sonication to a solution of Agg-A. As predicted, we obtained the single helical nanofibers of Agg-SH.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSeeded supramolecular polymerization.\u003c/b\u003e As mentioned, the metastable Agg-A was sonicated for 60 min at 283 K to produce short fragments of Agg-SH, so-called Agg-SH seed. The seeds show narrow length polydispersity (PDI, (\u003cem\u003eL\u003c/em\u003e\u003csub\u003e\u003cem\u003ew\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e/L\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e)\u0026thinsp;=\u0026thinsp;1.16) with a number-average length (L\u003csub\u003en\u003c/sub\u003e) of 250 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). When Agg-A and Agg-SH\u003csub\u003eseed\u003c/sub\u003e were mixed in a 1:50, 1:100, and 1:150 ratio ([Agg-SH\u003csub\u003eseed\u003c/sub\u003e]:[Agg-A]) at 308 K, the effective transformation of metastable Agg-A into Agg-SH was observed in CD spectra changes at 520 nm. Following the addition of Agg-SH\u003csub\u003eseed\u003c/sub\u003e to an excess amount of Agg-A, the supramolecular polymerization was initiated without a lag time and proceeded linearly with respect to the reaction time (Supplementary Fig.\u0026nbsp;22). The logarithm of the apparent polymerization rate, log(d(at 520 nm)/dt) and the amount of added Agg-SH\u003csub\u003eseed\u003c/sub\u003e were proportional with a slope of 1.05, indicating that the polymerization reaction is of first order with respect to Agg-SH\u003csub\u003eseed\u003c/sub\u003e (that is, chain-growth polymerization).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn contrast, the seeding experiments using Agg-SH\u003csub\u003eseed\u003c/sub\u003e did not initiate supramolecular polymerization under identical experimental conditions applied to kinetically trapped Agg-DH. This is due to the higher kinetic stability of Agg-DH compared to Agg-A. Thus, the concentration of Agg-SH\u003csub\u003eseed\u003c/sub\u003e was increased in the ratio of [Agg-SH]/ [Agg-DH] to reduce the kinetic stability of Agg-DH. Upon increasing the proportion of seed, the transformation of Agg-DH into Agg-SH was initiated without a lag time and proceeded linearly with respect to the reaction time (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). Additionally, the SEM images were taken after seeded experiments, in which the length of elongated single helical nanofibers was dependent on the ratio of Agg-SH\u003csub\u003eseed\u003c/sub\u003e, and the nanofibers were analyzed and visualized in histograms (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and Supplementary Fig.\u0026nbsp;23). Importantly, the length of obtained Agg-SH was proportional to the ratio of the total concentration of added Agg-SH\u003csub\u003eseed\u003c/sub\u003e to the initial concentration of Agg-DH, PDI values were ~\u0026thinsp;1.1 for all states. The resulting helicity followed that of Agg-SH\u003csub\u003eseed\u003c/sub\u003e. All these experimental results strongly indicate the living nature of the supramolecular polymerization of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e. These results indicate that the thermodynamic stability order is Agg-SH\u0026thinsp;\u0026gt;\u0026thinsp;Agg-DH\u0026thinsp;\u0026gt;\u0026thinsp;Agg-A.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn the present study, we have demonstrated the kinetically controlled self-assembly of Pt complex \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e, which exhibits transient helical inversion, into dynamic self-assembly with single and double helix structures. By precisely controlling the interplay between helical inversion and Pt-Pt interactions, we successfully navigated the pathway complexity, involving both interfiber and inter-molecular interactions under time evolution. The chiral building unit of \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e is attributed to the transient helical inversion between P-type Agg-A and M-type Agg-A as metastable states. This contributes to the suppression of spontaneous self-assembling processes. Therefore, the unique time evolution with transient helical inversion was found in kinetic analysis. Interestingly, in time evolution for Agg-DH at lower temperatures, the resulting kinetically trapped supramolecular polymers (Agg-DH) exhibited double helical structures via interfiber interactions with Pt-Pt interactions. Furthermore, the transformation into Agg-SH at higher temperatures is revealed to induce unexpected thermodynamically favored states of single helical structures by temperature programming-related activation barriers for pathway complexity in supramolecular polymerization. Selective pathway complexity was not only regulated by seeded living supramolecular polymerization but also controlled the length and helicity of the supramolecular polymers. By elucidating the kinetic control over pathway complexity in supramolecular polymerization, we provide valuable insights that can guide the rational design and engineering of functional materials with tailored properties. Through a combination of experimental investigations and theoretical analyses, this study offers a comprehensive understanding of the pathway complexity involved in supramolecular polymerization.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eMeasurements.\u0026nbsp;\u003c/strong\u003eThe \u003csup\u003e1\u003c/sup\u003eH and \u003csup\u003e13\u003c/sup\u003eC NMR spectra were taken on a Bruker DRX 300, DRX 500 and mass spectroscopy samples were analyzed on a LCQ Fleet Ion Trap Mass Spectrometer (Thermo fisher). A UV-visible spectrophotometer (Jasco V-750) was used to obtain the absorption spectra. IR spectra were observed over the range 500-4000 cm-1 with a Thermo Scientific Nicolet iS 10 instrument. The fluorescence spectra were obtained using a spectrophotometer (Jasco FP-8500).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCircular Dichroism (CD) Studies.\u0026nbsp;\u003c/strong\u003eThe CD spectra were recorded on a Jasco J-1500 CD spectrophotometer. The CD spectra were determined over the range of 250-800 nm using a quartz cell with 1.0 and 10.0 mm path lengths. Scans were taken at a rate of 500 nm/min with a sampling interval of 1 nm and a response time of 0.5s.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAtomic Force Microscopy (AFM) Studies\u003c/strong\u003e\u003cstrong\u003e.\u0026nbsp;\u003c/strong\u003eAFM measurements were performed by using an XE-100 and a PPP-NCHR 10 M cantilever (Park systems). The AFM samples were prepared by spin-coating (2000 rpm) onto freshly cleaved Muscovite Mica, and images were recorded with the AFM operating in a noncontact mode in the air at RT with a resolution of 1024 \u0026times; 1024 pixels, using moderate scan rates (0.3 Hz) and analyzed using XEI software developed by Park systems.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSEM observation\u003c/strong\u003e\u003cstrong\u003e.\u003c/strong\u003e FE-SEM images were observed using a Tescan (S8000). The images of samples using an accelerating voltage of 10 kV and an emission current of 8 \u0026mu;A. Samples were prepared by dropping solutions of supramolecular nanostructure on glasses, followed by spinning, drying, and coating them with a thin layer of Pt to increase the contrast.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCalculation of Avtivation Energy\u003c/strong\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eCD = CD\u003csub\u003e0\u003c/sub\u003e + (Plateau-CD\u003csub\u003e0\u003c/sub\u003e)*(1-exp (-k\u003csub\u003einv\u003c/sub\u003e*t))\u003c/p\u003e\n\u003cp\u003eWhere the value of CD\u003csub\u003e0\u003c/sub\u003e is the initial CD signal when time is zero, and Plateau is the CD value at infinite time.\u003c/p\u003e\n\u003cp\u003eThis equation is the result of considering the whole inversion process. In this way, the first step follows a pseudo-first-order kinetics where the k\u003csub\u003einv\u003c/sub\u003e can be obtained representing the ln(CD/CD\u003csub\u003e0\u003c/sub\u003e) vs. time for each temperature in the shortest times where the evolution of the CD follows a first-order kinetic process. \u003csup\u003e[52, 53]\u003c/sup\u003e After this, k\u003csub\u003einv\u003c/sub\u003e is the double assuming that both helices have the same energy.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eR value used is 8.314 J\u0026middot;K\u003csup\u003e\u0026minus;1\u003c/sup\u003e\u0026middot;mol\u003csup\u003e\u0026minus;1\u003c/sup\u003e, \u003cem\u003ek\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e = 1.381 \u0026times; 10\u003csup\u003e\u0026minus;23\u003c/sup\u003e J\u0026middot;K\u003csup\u003e\u0026minus;1\u003c/sup\u003e and h = 6.626 \u0026times; 10\u003csup\u003e\u0026minus;34\u003c/sup\u003e J\u0026middot;s\u003csup\u003e\u0026minus;1\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePreparation of Self-Assembled Samples.\u003c/strong\u003e The stock solution of monomeric \u003cstrong\u003e(\u003cem\u003eR\u003c/em\u003e)-1\u003c/strong\u003e was prepared in dimethyl sulfoxide (DMSO). The monomeric solution was then injected into the required volume of H2O to adjust the final concentration of the required choice. The final solvent mixture ratio of DMSO and H\u003csub\u003e2\u003c/sub\u003eO was 6:4 (v/v).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePreparation of seeds.\u003c/strong\u003e The seeds were prepared by applying sonication to aqueous solution of \u003cstrong\u003eAgg-A\u003c/strong\u003e at 10 \u0026deg;C. The \u003cstrong\u003eAgg-SH\u003c/strong\u003e seed was obtained via sonication at 10 \u0026deg;C for 1 hr (3 ml, 200 \u0026micro;M). By applying sonication, the Suparmolecular polymers fragmented into short pieces with relatively narrow length distribution were obtained, which was confirmed through analysis of SEM images, as shown in Fig.5 and Supplementary Fig.23\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIT) (Grant No. 2021R1A2C2007664, 2022R1A4A1022252, and RS-2023-00241926). This research was supported by Korea Basic Science Institute(National research Facilities and Equipment Center) grand funded by Ministry of Science and ICT.(No.RS-2024-00402475)\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contribution\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eJ. H. Jung.\u0026nbsp;and\u0026nbsp;S. H. Jung\u0026nbsp;conceived\u0026nbsp;the\u0026nbsp;idea\u0026nbsp;for\u0026nbsp;this\u0026nbsp;project.\u0026nbsp;H. M. Han.\u0026nbsp;and\u0026nbsp;M. J. Kim.\u0026nbsp;performed\u0026nbsp;the\u0026nbsp;experiments,\u0026nbsp;analyzed\u0026nbsp;the\u0026nbsp;data, and produced the artwork under the direction of J. H. Jung.\u0026nbsp;and\u0026nbsp;S. H. Jung.\u0026nbsp;All\u0026nbsp;authors\u0026nbsp;contributed\u0026nbsp;to\u0026nbsp;the manuscript.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary Information\u003c/strong\u003e The online version contains supplementary material at http://npg.nature.com/reprintsandpermissions/\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003ePeng, H. Q. \u003cem\u003eet al.\u003c/em\u003e Supramolecular polymers: recent advances based on the types of underlying interactions. \u003cem\u003eProg. Polym. Sci.\u003c/em\u003e \u003cstrong\u003e136\u003c/strong\u003e, 101635 (2023).\u003c/li\u003e\n \u003cli\u003eDe Greef, T. F. 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A. \u003cem\u003eet al.\u003c/em\u003e Supramolecular polymerization. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cstrong\u003e109\u003c/strong\u003e, 5687\u0026ndash;5754 (2009).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Scheme","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":false,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6654028/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6654028/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDesigning the organization of supramolecular systems with high-precision self-assembly along diverse pathways is a crucial strategy for optimizing functional properties. However, attaining this degree of control remains a significant challenge in the field. Here, we report the selective pathway dynamics of platinum (II) terpyridine-based complexes with \u003cem\u003e(R)\u003c/em\u003e-chiral side chains, which exhibit three distinct states (Agg-A, -DH, and -SH) in different pathways during the self-assembly process. Specifically, the Pt-complexes \u003cb\u003e(\u003c/b\u003e\u003cb\u003eR\u003c/b\u003e\u003cb\u003e)-1\u003c/b\u003e self-assemble into helical structures with opposite handedness as metastable Agg-A (M-type or P-type) depending on concentrations, which led to selective pathways due to transient helical inversion of Agg-A. Our kinetic experiments clearly demonstrated time- and temperature-dependent pathway dynamics. The kinetic observations at 308 K reveal the presence of a kinetically trapped aggregation (Agg-DH) with a double helix driven by interfiber interaction that forms via a transient helical inversion of metastable state (Agg-A) as an on-pathway intermediate (P-type). At 333 K, a thermodynamically favored aggregation (Agg-SH) with a single helix emerges from the metastable state Agg-A as an off-pathway intermediate. Interestingly, the metastable Agg-A can follow two different pathways depending on temperatures, leading to either Agg-DH or Agg-SH. Eventually, both distinct metastable state (Agg-A) and kinetically trapped state (Agg-DH) transform into thermodynamically stable state (Agg-SH). Furthermore, seeded-living supramolecular polymerization was conducted to demonstrate selective pathway control. This study demonstrates the control over pathway complexity and their unique morphological evolution driven by transient helical inversion, as well as interfiber and intermolecular Pt-Pt interactions.\u003c/p\u003e","manuscriptTitle":"Selective pathway dynamics of transient helical inversion in supramolecular polymers under non-equilibrium conditions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-23 16:08:35","doi":"10.21203/rs.3.rs-6654028/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b0b7370a-1acf-44f1-acaf-3d398b910fa1","owner":[],"postedDate":"May 23rd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":48833775,"name":"Physical sciences/Chemistry/Supramolecular chemistry/Supramolecular polymers"},{"id":48833776,"name":"Physical sciences/Materials science/Nanoscale materials/Molecular self-assembly"}],"tags":[],"updatedAt":"2026-01-15T15:11:55+00:00","versionOfRecord":[],"versionCreatedAt":"2025-05-23 16:08:35","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6654028","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6654028","identity":"rs-6654028","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}