Photoresponsive Supramolecular Polymers Capable of Intrachain Folding and Interchain Aggregation.

The competition between polymer chain folding and aggregation is a critical structuring process that determines the physical properties of synthetic and biopolymers. However, supramolecular polymer systems that exhibit both processes have not yet been reported. We herein introduce a system in which folded supramolecular polymers spontaneously undergo interchain aggregation due to a rearrangement in internal molecular order, converting them into crystalline aggregates. These folded supramolecular polymers slowly crystallize over the course of half a day, due to their characteristic higher-order structures. However, the photoisomerization of the trans-azobenzene incorporated into the monomer to the cis isomer leads to unfolding of the polymer, accelerating the intrachain and interchain molecular ordering to a few hours. The intermediate structures visualized by AFM demonstrate that the unfolding is coupled with interchain aggregation.

Toroid-rod supramolecular polymorphism derived from conformational isomerism of a π-conjugated system.

Hydrogen-bonded supermacrocycles (rosettes) composed of dinaphthylethene π-conjugated systems show unique supramolecular polymorphism affording nanorings and nanorods via kinetically controlled self-assembly. Molecular modeling and molecular dynamics simulations proposed that conformational isomerism of the π-conjugated systems leads to planar and convex rosette geometries, which results in their distinct stacking arrangements.

Impact of Ring-Closing on the Photophysical Properties of One-Dimensional π-Conjugated Molecular Aggregate.

The self-assembled state of molecules plays a pivotal role in determining how inherent molecular properties transform and give rise to supramolecular functionalities and has long attracted attention. However, understanding the influence of morphologies spanning the nano- to mesoscopic scales of supramolecular assemblies derived from identical intermolecular interactions has been notoriously challenging due to dynamic structural change and monomer exchange of assemblies in solution. In this study, we demonstrate that curved one-dimensional molecular assemblies (supramolecular polymers) of lengths of around 70-200 nm, originating from the same luminescent molecule, exhibit distinct photoluminescent properties when they form closed circular structures (toroids) versus when they possess chain termini in solution (random coils). By exploiting the difference in kinetic stability between the toroids and random coils, we developed a dialysis protocol to selectively purify the former. It was revealed that these terminus-free closed structures manifest higher energy and more efficient luminescence compared with their mixed state with random coils. Time-resolved fluorescence measurements unveiled that random coils, due to their dynamic structural fluctuation in solution, generate local defects throughout the main chain, leading to luminescence from lower energy levels. In mixtures of the two assemblies, luminescence was exclusively observed from such a lower energy level of random coils, a result attributed to energy transfer between the assemblies. This work emphasizes that for identical supramolecular assemblies, only averaged properties have traditionally been considered, but their structures at the nano- to mesoscopic scale are important especially if they have a certain degree of shape persistency even in solution.

Supramolecular Polymer Polymorphism: Spontaneous Helix-Helicoid Transition through Dislocation of Hydrogen-Bonded π-Rosettes.

Polymorphism, a phenomenon whereby disparate self-assembled products can be formed from identical molecules, has incited interest in the field of supramolecular polymers. Conventionally, the monomers that constitute supramolecular polymers are engineered to facilitate one-dimensional aggregation and, consequently, their polymorphism surfaces primarily when the states of assembly differ significantly. This engenders polymorphs of divergent dimensionalities such as one- and two-dimensional aggregates. Notwithstanding, realizing supramolecular polymer polymorphism, wherein polymorphs maintain one-dimensional aggregation, persists as a daunting challenge. In this work, we expound upon the manifestation of two supramolecular polymer polymorphs formed from a large discotic supramolecular monomer (rosette), which consists of six hydrogen-bonded molecules with an extended π-conjugated core. These polymorphs are generated in mixtures of chloroform and methylcyclohexane, attributable to distinctly different disc stacking arrangements. The face-to-face (minimal displacement) and offset (large displacement) stacking arrangements can be predicated on their distinctive photophysical properties. The face-to-face stacking results in a twisted helix structure. Conversely, the offset stacking induces inherent curvature in the supramolecular fiber, thereby culminating in a hollow helical coil (helicoid). While both polymorphs exhibit bistability in nonpolar solvent compositions, the face-to-face stacking attains stability purely in a kinetic sense within a polar solvent composition and undergoes conversion into offset stacking through a dislocation of stacked rosettes. This occurs without the dissociation and nucleation of monomers, leading to unprecedented helicoidal folding of supramolecular polymers. Our findings augment our understanding of supramolecular polymer polymorphism, but they also highlight a distinctive method for achieving helicoidal folding in supramolecular polymers.

A Coformer Approach for Supramolecular Polymerization at High Concentrations.

Insolubility of functional molecules caused by polymorphism sometimes poses limitations for their solution-based processing. Such a situation can also occur in the preparation processes of supramolecular polymers formed in a solution. An effective strategy to address this issue is to prepare amorphous solid states by introducing a "coformer" molecule capable of inhibiting the formation of an insoluble polymorph through co-aggregation. Herein, inspired by the coformer approach, we demonstrated a solubility enhancement of a barbiturate π-conjugated compound that can supramolecularly polymerize through six-membered hydrogen-bonded rosettes. Our newly synthesized supramolecular coformer molecule features a sterically demanding methyl group in the π-conjugated unit of the parent molecule. Although the parent molecule exhibits low solubility in nonpolar solvents due to the formation of a crystalline polymorph comprising a tape-like hydrogen-bonded array prior to the supramolecular polymerization, mixing with the coformer compound enhanced the solubility by inhibiting mesoscopic organization of the tapes. The two monomers were then co-polymerized into desired helicoidal supramolecular polymers through the formation of heteromeric rosettes.

Distinct seed topologies enable comparison of elongation and secondary nucleation pathways in seeded supramolecular polymerization.

The influence of seed topologies on seeded supramolecular polymerization was examined using helicoidal and toroidal supramolecular polymer seeds. The addition of these seeds to a supersaturated solution of monomers led to distinct nucleation-growth kinetics, which were attributed to the significant difference between the elongation from helicoid termini and secondary nucleation catalyzed by the toroid surface.

Fine-tuning of the size of supramolecular nanotoroids suppresses the subsequent catenation of nano-[2]catenane.

A judicious combination of ring-closing supramolecular polymerization and secondary nucleation can hierarchically organize a diphenylnaphthalene barbiturate monomer bearing a 3,4,5-tri(dodecyloxy)benzyloxy unit into self-assembled nano-polycatenanes composed of nanotoroids. In our previous study, nano-polycatenanes of variable length have been formed uncontrollably from the monomer that provides nanotoroids with sufficiently wide inner void space wherein secondary nucleation is driven by non-specific solvophobic interaction. In this study, we found that the elongation of the alkyl chain length of the barbiturate monomer decreases the inner void space of nanotoroids while increasing the frequency of secondary nucleation. These two effects resulted in an increase in the yield of nano-[2]catenane. This unique property observed in our self-assembled nanocatenanes might be extended to a controlled synthesis of covalent polycatenanes using non-specific interactions.

Amplification of Molecular Asymmetry during the Hierarchical Self-Assembly of Foldable Azobenzene Dyads into Nanotoroids and Nanotubes.

The amplification of molecular asymmetry through self-assembly is a phenomenon that not only comprehends the origin of homochirality in nature but also produces chiroptically active functional materials from molecules with minimal enantiomeric purity. Understanding how molecular asymmetry can be transferred and amplified into higher-order structures in a hierarchical self-assembly system is important but still unexplored. Herein, we present an intriguing example of the amplification of molecular asymmetry in hierarchically self-assembled nanotubes that feature discrete and isolatable toroidal intermediates. The hierarchical self-assembly is initiated via asymmetric intramolecular folding of scissor-shaped azobenzene dyads furnished with chiral side chains. When scalemic mixtures of the enantiomers are dissolved in a non-polar solvent and cooled to 20 °C, single-handed nanotoroids are formed, as confirmed using atomic force microscopy and circular dichroism analyses. A strong majority-rules effect at the nanotoroid level is observed and can be explained by a low mismatch penalty and a high helix-reversal penalty. The single-handed nanotoroids stack upon cooling to 0 °C to exclusively afford their respective single-handed nanotubes. Thus, the same degree of amplification of molecular asymmetry is realized at the nanotube level. The internal packing efficiency of molecules within nanotubes prepared from the pure enantiomers or their scalemic mixtures is likely different, as suggested by the absence of higher-order structure (supercoil) formation in the latter. X-ray diffraction analysis of the anisotropically oriented nanotube films revealed looser molecular packing within the scalemic nanotubes, which clearly reflects the lower enantiomeric purity of their internal chiral side chains.

Supramolecular polymerization of thiobarbituric acid naphthalene dye.

2-Thiobarbituric acid-functionalized naphthalene dye selectively self-assembles into crystalline fibers to show material properties that are different from those of a previously reported oxo-barbituric acid derivative affording curved supramolecular polymers via the formation of hydrogen-bonded rosettes. Detailed studies using 1H-NMR, DFT calculation and X-ray diffraction revealed that the crystalline fiber is formed through a tape-like hydrogen-bonding pattern due to the weaker hydrogen-bond-acceptor ability of the thiocarbonyl group.

Harmonizing Topological Features of Self-Assembled Fibers by Rosette-Mediated Random Supramolecular Copolymerization and Self-Sorting of Monomers by Photo-Cross-Linking.

Random copolymerization is an effective approach to synthesize the desired polymers by harmonizing distinct properties of different monomers. For supramolecular polymers in which monomer binding is inherently dynamic, it is difficult to achieve random copolymerization of monomers with distinct molecular structures and properties due to an enthalpic advantage upon self-recognition (self-sorting). Herein, we demonstrate an example of thermodynamically controlled random supramolecular copolymerization of two monomers functionalized with barbituric acid via the formation of six-membered hydrogen-bonded rosette intermediates to exhibit structural harmonization of the two main-chain motifs, i.e., intrinsically curved and linear motifs. One monomer based on naphthalene chromophore exclusively forms toroidal fibers, whereas another one bearing additional photoreactive diacetylene moiety affords linearly elongated fibers. Supramolecular copolymerization of the two monomers is achieved by cooling hot monomer mixtures in a nonpolar solvent, which results in the formation of thermodynamically stable spirally folded yet elongated fibers. Atomic force microscopic observations and theoretical simulations of the experimental data obtained by absorption spectroscopy reveal the homopolymerization of the diacetylene-functionalized monomer in the high-temperature region, followed by the incorporation of the naphthalene monomer in the medium-temperature region to form supramolecular copolymers with random monomer sequence. Finally, we demonstrate that the random copolymerization process can be switched to a narcissistically self-sorting one by deactivating monomer exchange through the photo-cross-linking of the diacetylene-functionalized monomers.

Photo-modulation of supramolecular polymorphism in the self-assembly of a scissor-shaped azobenzene dyad into nanotoroids and fibers.

Recent advances in the research field of supramolecularly engineered dye aggregates have enabled the design of simple one-dimensional stacks such as fibers and of closed structures such as nanotoroids (nanorings). More complex and advanced supramolecular systems could potentially be designed using a molecule that is able to provide either of these distinct nanostructures under different conditions. In this study, we introduced bulky but strongly aggregating cholesterol units to a scissor-shaped azobenzene dyad framework, which affords either nanotoroids, nanotubes, or 1D fibers, depending on the substituents. This new dyad with two trans-azobenzene arms shows supramolecular polymorphism in its temperature-controlled self-assembly, leading to not only oligomeric nanotoroids as kinetic products, but also to one-dimensional fibers as thermodynamic products. This supramolecular polymorphism can also be achieved via photo-triggered self-assembly, i.e., irradiation of a monomeric solution of the dyad with two cis-azobenzene arms using strong visible light leads to the preferential formation of nanotoroids, whereas irradiation with weak visible light leads to the predominant formation of 1D fibers. This is the first example of a successful light-induced modulation of supramolecular polymorphism to produce distinctly nanostructured aggregates under isothermal conditions.

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems.

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π-π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π-π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units. In CHCl3, both compounds are molecularly dissolved and accordingly poorly emissive due to a torsion-induced non-radiative decay. In methylcyclohexane-rich conditions, these barbiturates self-assemble to form crystalline nanofibers and exhibit strongly enhanced emission through supramolecular polymerization driven by hydrogen-bonding. Our structural analysis suggests that the barbiturates form a tape-like hydrogen-bonding motif, which is rationalized by considering that the twisted geometries of 2,3-diphenylthiophene cores prevend the competing rosettes from stacking into columnar supramolecular polymers. We also found that a small difference in the molecular polarity originating from the substitutional position of the thiophene core influences interchain association of the supramolecular polymers, affording different luminescent soft materials, gel and nanosheet.

Biasing the Hierarchy Motifs of Nanotoroids: from 1D Nanotubes to 2D Porous Networks.

Hierarchical organization of self-assembled structures into superstructures is omnipresent in Nature but has been rarely achieved in synthetic molecular assembly due to the absence of clear structural rules. We herein report on the self-assembly of scissor-shaped azobenzene dyads which form discrete nanotoroids that further organize into 2D porous networks. The steric demand of the peripheral aliphatic units diminishes the trend of the azobenzene dyad to constitute stackable nanotoroids in solution, thus affording isolated (unstackable) nanotoroids upon cooling. Upon drying, these nanotoroids organize at graphite surface to form well-defined 2D porous networks. The photoirradiation with UV and visible light enabled reversible dissociation and reconstruction of nanotoroids through the efficient trans↔cis isomerization of azobenzene moieties in solution.

Scissor-Shaped Photochromic Dyads: Hierarchical Self-Assembly and Photoresponsive Property.

Unique relationships between hierarchically organized biological nanostructures and functions have motivated chemists to construct sophisticated artificial nanostructured systems from small and simple synthetic molecules through self-assembly. As one of such sophisticated systems, we have investigated scissor-shaped photochromic dyads that can hierarchically self-assemble into discrete nanostructures showing photoresponsive properties. We synthesized various azobenzene dyads and found that these dyads adopt intramolecularly folded conformation like a closed scissor, and then self-assemble into toroidal nanostructures by generating curvature. The toroids further organize into nanotubes and further into helical supramolecular fibers depending on the nature of alkyl substituents. All of these nanostructures can be dissociated and reorganized through the photoisomerization of azobenzene units. On the other hand, the introduction of stilbene chromophores instead of azobenzenes leads to one-dimensional supramolecular polymerization, which upon the intramolecular photocyclization of stilbene chromophores shifts to curved self-assembly leading to helicoidal fibers with distinct supramolecular chirality.

Non-uniform Photoinduced Unfolding of Supramolecular Polymers Leading to Topological Block Nanofibers.

Synthesis of one-dimensional nanofibers with distinct topological (higher-order structural) domains in the same main chain is one of the challenging topics in modern supramolecular polymer chemistry. Non-uniform structural transformation of supramolecular polymer chains by external stimuli may enable preparation of such nanofibers. To demonstrate feasibility of this post-polymerization strategy, we prepared a photoresponsive helically folded supramolecular polymers from a barbiturate monomer containing an azobenzene-embedded rigid π-conjugated scaffold. In contrast to previous helically folded supramolecular polymers composed of a more flexible azobenzene monomer, UV-light induced unfolding of the newly prepared helically folded supramolecular polymers occurred nonuniformly, affording topological block copolymers consisting of folded and unfolded domains. The formation of such blocky copolymers indicates that the photoinduced unfolding of the helically folded structures initiates from relatively flexible parts such as termini or defects. Spontaneous refolding of the unfolded domains was observed after visible-light irradiation followed by aging to restore fully folded structures.

Wavy supramolecular polymers formed by hydrogen-bonded rosettes.

A barbiturate-functionalized supramolecular monomer bearing an ester-linked biphenyl and azobenzene π-conjugated core affords wavy supramolecular polymers. The periodic inversion of curvature is due to the conformational rigidity of the monomer and repulsive interactions between rosettes. Photoisomerization of the azobenzene moiety increases the fragility of the main chain without deteriorating its periodic structure.

Diarylethene-Powered Light-Induced Folding of Supramolecular Polymers.

Helical folding of randomly coiled linear polymers is an essential organization process not only for biological polypeptides but also for synthetic functional polymers. Realization of this dynamic process in supramolecular polymers (SPs) is, however, a formidable challenge because of their inherent lability of main chains upon changing an external environment that can drive the folding process (e.g., solvent, concentration, and temperature). We herein report a photoinduced reversible folding/unfolding of rosette-based SPs driven by photoisomerization of a diarylethene (DAE). Temperature-controlled supramolecular polymerization of a barbiturate-functionalized DAE (open isomer) in nonpolar solvent results in the formation of intrinsically curved, but randomly coiled, SPs due to the presence of defects. Irradiation of the randomly coiled SPs with UV light causes efficient ring-closure reaction of the DAE moieties, which induces helical folding of the randomly coiled structures into helicoidal ones, as evidenced by atomic force microscopy and small-angle X-ray scattering. The helical folding is driven by internal structure ordering of the SP fiber that repairs the defects and interloop interaction occurring only for the resulting helicoidal structure. In contrast, direct supramolecular polymerization of the ring-closed DAE monomers by temperature control affords linearly extended ribbon-like SPs lacking intrinsic curvature that are thermodynamically less stable compared to the helicoidal SPs. The finding represents an important concept applicable to other SP systems; that is, postpolymerization (photo)reaction of preorganized kinetic structures can lead to more thermodynamically stable structures that are inaccessible directly through temperature-controlled protocols.

Self-assembly of alkylated and perfluoroalkylated scissor-shaped azobenzene dyads into distinct structures.

Scissor-shaped azobenzene dyads possessing alkyl side chains can hierarchically self-assemble through a folded conformation into toroidal and tubular nanostructures. We found that the introduction of perfluoroalkyl side chains transforms the assembly pathway into direct one-dimensional stacking of the folded conformer, resulting in the formation of gel-forming supramolecular fibers that can reversibly dissociate and reassemble on exposure to light.