Supramolecular polymers form tactoids through liquid-liquid phase separation.

Liquid-liquid phase separation (LLPS) of biopolymers has recently been shown to play a central role in the formation of membraneless organelles with a multitude of biological functions1-3. The interplay between LLPS and macromolecular condensation is part of continuing studies4,5. Synthetic supramolecular polymers are the non-covalent equivalent of macromolecules but they are not reported to undergo LLPS yet. Here we show that continuously growing fibrils, obtained from supramolecular polymerizations of synthetic components, are responsible for phase separation into highly anisotropic aqueous liquid droplets (tactoids) by means of an entropy-driven pathway. The crowding environment, regulated by dextran concentration, affects not only the kinetics of supramolecular polymerizations but also the properties of LLPS, including phase-separation kinetics, morphology, internal order, fluidity and mechanical properties of the final tactoids. In addition, substrate-liquid and liquid-liquid interfaces proved capable of accelerating LLPS of supramolecular polymers, allowing the generation of a myriad of three-dimensional-ordered structures, including highly ordered arrays of micrometre-long tactoids at surfaces. The generality and many possibilities of supramolecular polymerizations to control emerging morphologies are demonstrated with several supramolecular polymers, opening up a new field of matter ranging from highly structured aqueous solutions by means of stabilized LLPS to nanoscopic soft matter.

Supramolecular Polymerization as a Tool to Reveal the Magnetic Transition Dipole Moment of Heptazines.

Heptazine derivatives have attracted significant interest due to their small S1-T1 gap, which contributes to their unique electronic and optical properties. However, the nature of the lowest excited state remains ambiguous. In the present study, we characterize the lowest optical transition of heptazine by its magnetic transition dipole moment. To measure the magnetic transition dipole moment, the flat heptazine must be chiroptically active, which is difficult to achieve for single heptazine molecules. Therefore, we used supramolecular polymerization as an approach to make homochiral stacks of heptazine derivatives. Upon formation of the supramolecular polymers, the preferred helical stacking of heptazine introduces circular polarization of absorption and fluorescence. The magnetic transition dipole moments for the S1 ← S0 and S1 → S0 are determined to be 0.35 and 0.36 Bohr magneton, respectively. These high values of magnetic transition dipole moments support the intramolecular charge transfer nature of the lowest excited state from nitrogen to carbon in heptazine and further confirm the degeneracy of S1 and T1.

Consequences of Vibrational Strong Coupling on Supramolecular Polymerization of Porphyrins.

Supramolecular polymers display interesting optoelectronic properties and, thus, deploy multiple applications based on their molecular arrangement. However, controlling supramolecular interactions to achieve a desirable molecular organization is not straightforward. Over the past decade, light-matter strong coupling has emerged as a new tool for modifying chemical and material properties. This novel approach has also been shown to alter the morphology of supramolecular organization by coupling the vibrational bands of solute and solvent to the optical modes of a Fabry-Perot cavity (vibrational strong coupling, VSC). Here, we study the effect of VSC on the supramolecular polymerization of chiral zinc-porphyrins (S-Zn) via a cooperative effect. Electronic circular dichroism (ECD) measurements indicate that the elongation temperature (Te) of the supramolecular polymerization is lowered by ∼10 °C under VSC. We have also generalized this effect by exploring other supramolecular systems under strong coupling conditions. The results indicate that the solute-solvent interactions are modified under VSC, which destabilizes the nuclei of the supramolecular polymer at higher temperatures. These findings demonstrate that the VSC can indeed be used as a tool to control the energy landscape of supramolecular polymerization. Furthermore, we use this unique approach to switch between the states formed under ON- and OFF-resonance conditions, achieved by simply tuning the optical cavity in and out of resonance.

Self-Assembly of Discrete Oligomers of Naphthalenediimides in Bulk and on Surfaces.

Here, we report on the synthesis of discrete oligomers of alkyl-bridged naphthalenediimides (NDIs) and study their molecular nanostructures both in bulk, in solution, and at the liquid-solid interface. Via an iterative synthesis method, multiple NDI cores were bridged with short and saturated alkyl-diamines (C3 and C12 ) or long and unsaturated alkyl-diamines (u2 C33 to u8 C100 ) at their imide termini. The strong intermolecular interaction between the NDI cores was observed by probing their photophysical properties in solution. In bulk, the discrete NDI oligomers preferentially ordered in lamellar morphologies, irrespective of whether a saturated or unsaturated spacer was employed. Moreover, both the molecular architecture as well as the crystallization conditions play a significant role in the nanoscale ordering. The long unsaturated alkyl chains lead preferably to folded-chain conformations while their saturated analogues form stretched arrangements. At the solution-solid interface, well-defined lamellar regions were observed. These results show that precision in chemical structure alone is not sufficient to reach well-defined structures of discrete oligomers, but that it must be combined with precision in processing conditions.

Functionalization of Supramolecular Polymers by Dynamic Covalent Boroxine Chemistry.

Molecular scaffolds that enable the combinatorial synthesis of new supramolecular building blocks are promising targets for the construction of functional molecular systems. Here, we report a supramolecular scaffold based on boroxine that enables the formation of chiral and ordered 1D supramolecular polymers, which can be easily functionalized for circularly polarized luminescence. The boroxine monomers are quantitatively synthesized in situ, both in bulk and in solution, from boronic acid precursors and cooperatively polymerize into 1D helical aggregates stabilized by threefold hydrogen-bonding and π-π stacking. We then demonstrate amplification of asymmetry in the co-assembly of chiral/achiral monomers and the co-condensation of chiral/achiral precursors in classical and in situ sergeant-and-soldiers experiments, respectively, showing fast boronic acid exchange reactions occurring in the system. Remarkably, co-condensation of pyrene boronic acid with a hydrogen-bonding chiral boronic acid results in chiral pyrene aggregation with circularly polarized excimer emission and g-values in the order of 10-3. Yet, the electron deficiency of boron in boroxine makes them chemically addressable by nucleophiles, but also sensitive to hydrolysis. With this sensitivity in mind, we provide first insights into the prospects offered by boroxine-based supramolecular polymers to make chemically addressable, functional, and adaptive systems.

Solvent-Induced Pathway Complexity of Supramolecular Polymerization Unveiled Using the Hansen Solubility Parameters.

Supramolecular building blocks assembling into helical aggregates are ubiquitous in the current literature, yet the role of solvents in these supramolecular polymerizations often remains elusive. Here, we present a systematic study that quantifies solvent-supramolecular polymer compatibility using the Hansen solubility parameters (δD, δH, and δP). We first studied the solubility space of the supramolecular building block triazine-1,3,5-tribenzenecarboxamide S-T. Due to its amphiphilic nature, a dual-sphere model based on 58 solvents was applied describing the solubility space of the monomeric state (green sphere) and supramolecular polymer state (blue sphere). To our surprise, further in-depth spectroscopic and morphological studies unveiled a distinct solubility region in-between the two spheres giving rise to the formation of higher-order aggregated structures. This phenomenon occurs due to subtle differences in polarity between the solvent and the side chains and highlights the solvent-induced pathway complexity of supramolecular polymerizations. Subsequent variations in concentration and temperature led to the expansion and contraction of both solubility spheres providing two additional features to tune the monomer and supramolecular polymer solubility. Finally, we applied our dual-sphere model on structurally disparate monomers, such as Zn-porphyrin (S-P) and triphenylamine (S-A), demonstrating the generality of the model and the importance of the supramolecular monomer design in connection with the solvent used. This work unravels the solvent-induced pathway complexity of discotic supramolecular building blocks using a parametrized approach in which interactions between the solvent and solute play a crucial role.

Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification.

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.

Simulating Assembly Landscapes for Comprehensive Understanding of Supramolecular Polymer-Solvent Systems.

Complexity in supramolecular polymer systems arises from interactions between different components, including solvent molecules. By varying their concentration or temperature in such multicomponent systems, complex phenomena can occur such as thermally bisignate and dilution-induced assembly of supramolecular polymers. Herein, we demonstrate that both these phenomena emerge from the same underlying interaction mechanism between the components. As a model system, amide-decorated supramolecular polymers of porphyrins were investigated in combination with aliphatic alcohols as hydrogen-bond scavengers, and thermodynamic mass-balance models were applied to map the three-dimensional assembly landscapes. These studies unveiled that the interaction between hydrogen-bond scavengers and monomers is temperature-dependent and becomes dominant at high monomer concentrations. With these insights, we could exploit competitive monomer-alcohol interactions to prompt the dilution-induced assembly of various common monomers as well as bisignate assembly events. Moreover, kinetic insights were obtained by navigating through the assembly landscape. Similar to phase diagrams of covalent polymers, these assembly landscapes provide a comprehensive picture of supramolecular polymerizations, which helps to precisely regulate the system properties. The generality of this approach using assembly landscapes makes it relevant for any supramolecular system, and this enhanced control will open the door to build complex and functional supramolecular polymer systems.

Temperature Directs the Majority-Rules Principle in Supramolecular Copolymers Driven by Triazine-Benzene Interactions.

Supramolecular copolymers have typically been studied in the extreme cases, such as self-sorting or highly mixed copolymer systems, while the intermediate systems have been less understood. We have reported the temperature-dependent microstructure in copolymers of triazine- and benzene-derivatives based on charge-transfer interactions with a highly alternating microstructure at low temperatures. Here, we investigate the temperature-dependent copolymerization further and increase the complexity by combining triazine- and benzene-derivatives with opposite preferred helicities. In this case, intercalation of the benzene-derivative into the triazine-derivative assemblies causes a helical inversion. The inversion of the net helicity was rationalized by comparing the mismatch penalties of the individual monomers, which indicated that the benzene-derivative dictates the helical screw-sense of the supramolecular copolymers. Surprisingly, this was not reflected in further investigations of slightly modified triazine- and benzene-derivatives, thus highlighting that the outcome is a subtle balance between structural features, where small differences can be amplified due to the competitive nature of the interactions. Overall, these findings suggest that the temperature-dependent microstructure of triazine- and benzene-based supramolecular copolymers determines the copolymer helicity of the presented system in a similar way as the mixed majority-rules phenomenon.

Making waves in a photoactive polymer film.

Oscillating materials that adapt their shapes in response to external stimuli are of interest for emerging applications in medicine and robotics. For example, liquid-crystal networks can be programmed to undergo stimulus-induced deformations in various geometries, including in response to light. Azobenzene molecules are often incorporated into liquid-crystal polymer films to make them photoresponsive; however, in most cases only the bending responses of these films have been studied, and relaxation after photo-isomerization is rather slow. Modifying the core or adding substituents to the azobenzene moiety can lead to marked changes in photophysical and photochemical properties, providing an opportunity to circumvent the use of a complex set-up that involves multiple light sources, lenses or mirrors. Here, by incorporating azobenzene derivatives with fast cis-to-trans thermal relaxation into liquid-crystal networks, we generate photoactive polymer films that exhibit continuous, directional, macroscopic mechanical waves under constant light illumination, with a feedback loop that is driven by self-shadowing. We explain the mechanism of wave generation using a theoretical model and numerical simulations, which show good qualitative agreement with our experiments. We also demonstrate the potential application of our photoactive films in light-driven locomotion and self-cleaning surfaces, and anticipate further applications in fields such as photomechanical energy harvesting and miniaturized transport.

Circular depolarization spectroscopy: A new tool to study photo-imprinting of chirality.

When irradiating a molecular material containing photo-isomerizable groups with pure circularly polarized light, a particular handedness may get imprinted into the material. To study the mechanism and kinetics of this process in situ and operando, we have developed a new chiroptical tool where the circular polarization of the incident circularly polarized light is monitored after transmission through the photoactive layer. Practical limits to the resolution and sensitivity of the measurements as well as its calibration are discussed. To aid interpretation of experimental results, we present kinetic Monte Carlo simulations on a model for the active material involving photo-induced reorientation of molecules in a cholesteric organization. The simulations support the interpretation of a transient minimum in the degree of circular polarization of the transmitted light in terms of a nematic transient state during photo-inversion of a cholesteric organization in the molecular material.

Coupled liquid crystalline oscillators in Huygens' synchrony.

In the flourishing field of soft robotics, strategies to embody communication and collective motion are scarce. Here we report the synchronized oscillations of thin plastic actuators by an approach reminiscent of the synchronized motion of pendula and metronomes. Two liquid crystalline network oscillators fuelled by light influence the movement of one another and display synchronized oscillations in-phase and anti-phase in a steady state. By observing entrainment between the asymmetric oscillators we demonstrate the existence of coupling between the two actuators. We qualitatively explain the origin of the synchronized motion using a theoretical model and numerical simulations, which suggest that the motion can be tuned by the mechanical properties of the coupling joint. We thus anticipate that the complex synchronization phenomena usually observed in rigid systems can also exist in soft polymeric materials. This enables the use of new stimuli, featuring an example of collective motion by photo-actuation.

In situ Synthesis of Supramolecular Polymers: Finding the Right Conditions when Combining Covalent and Non-Covalent Synthesis.

The combination of covalent and non-covalent synthesis is omnipresent in nature and potentially enables access to new materials. Yet, the fundamental principles that govern such a synthesis are barely understood. Here, we demonstrate how even simple reaction mixtures behave surprisingly complex when covalent reactions are coupled to self-assembly processes. Specifically, we study the reaction behavior of a system in which the in situ formation of discotic benzene-1,3,5-tricarboxamide (BTA) monomers is linked to an intertwined non-covalent reaction network including self-assembly into helical BTA polymers. This system shows an unexpected phase-separation behavior in which an interplay of reactant/product concentrations, side-products and solvent purity determines the system composition. We envision that these insights can bring us one step closer to how to design the synthesis of systems in a combined covalent/non-covalent fashion.

Photo-Imprinting of the Helical Organization in Liquid-Crystal Networks Using Achiral Monomers and Circularly Polarized Light.

Control over molecular motion is facilitated in materials with highly ordered nanoscale structures. Here we report on the fabrication of cholesteric liquid-crystal networks by circularly polarized light irradiation, without the need for chiral dopant or plasticizer. The polymer network is obtained by photopolymerization of a smectic achiral diacrylate mesogen consisting of an azobenzene core and discrete oligodimethylsiloxane tails. The synchronous helical photoalignment and photopolymerization originate from the cooperative movement of the mesogens ordered in well-defined responsive structures, together with the flexibility of the oligodimethylsiloxane blocks. The resulting thin films show excellent thermal stability and light-induced memory features with reversible responses. Additionally, we demonstrate the fabrication of photo-patterned films of liquid-crystal networks with opposite helical senses. These findings provide a new method to make light-controllable chiroptical materials with exciting applications in optics and photonics.

How Subtle Changes Can Make a Difference: Reproducibility in Complex Supramolecular Systems.

The desire to construct complex molecular systems is driven by the need for technological (r)evolution and our intrinsic curiosity to comprehend the origin of life. Supramolecular chemists tackle this challenge by combining covalent and noncovalent reactions leading to multicomponent systems with emerging complexity. However, this synthetic strategy often coincides with difficult preparation protocols and a narrow window of suitable conditions. Here, we report on unsuspected observations of our group that highlight the impact of subtle "irregularities" on supramolecular systems. Based on the effects of pathway complexity, minute amounts of water in organic solvents or small impurities in the supramolecular building block, we discuss potential pitfalls in the study of complex systems. This article is intended to draw attention to often overlooked details and to initiate an open discussion on the importance of reporting experimental details to increase reproducibility in supramolecular chemistry.

Unraveling the Complexity of Supramolecular Copolymerization Dictated by Triazine-Benzene Interactions.

Supramolecular copolymers formed by the noncovalent synthesis of multiple components expand the complexity of functional molecular systems. However, varying the composition and microstructure of copolymers through tuning the interactions between building blocks remains a challenge. Here, we report a remarkable discovery of the temperature-dependent supramolecular copolymerization of the two chiral monomers 4,4',4″-(1,3,5-triazine-2,4,6-triyl)tribenzamide (S-T) and 4,4',4″-(benzene-1,3,5-triyl)tribenzamide (S-B). We first demonstrate in the homopolymerization of the two individual monomers that a subtle change from the central triazine to benzene in the chemical structure of the monomers significantly affects the properties of the resulting homopolymers in solution. Homopolymers formed by S-T exhibit enhanced stability in comparison to S-B. More importantly, through a combination of spectroscopic analysis and theoretical simulation, we reveal the complex process of copolymerization: S-T aggregates into homopolymers at elevated temperature, and upon slow cooling S-B gradually intercalates into the copolymers, to finally give copolymers with almost 80% alternating bonds at 10 °C. The formation of the predominantly alternating copolymers is plausibly contributed by preferred heterointeractions between triazine and benzene cores in S-T and S-B, respectively, at lower temperatures. Overall, this work unravels the complexity of a supramolecular copolymerization process where an intermediate heterointeraction (higher than one homointeraction and lower than the other homointeraction) presents and proposes a general method to elucidate the microstructures of copolymers responsive to temperature changes.

Spin Filtering in Supramolecular Polymers Assembled from Achiral Monomers Mediated by Chiral Solvents.

In past studies, spin selective transport was observed in polymers and supramolecular structures that are based on homochiral building blocks possessing stereocenters. Here we address the question to what extent chiral building blocks are required for observing the chiral induced spin selectivity (CISS) effect. We demonstrate the CISS effect in supramolecular polymers exclusively containing achiral monomers, where the supramolecular chirality was induced by chiral solvents that were removed from the fibers before measuring. Spin-selective transport was observed for electrons transmitted perpendicular to the fibers' long axis. The spin polarization correlates with the intensity of the CD spectra of the polymers, indicating that the effect is nonlocal. It is found that the spin polarization increases with the samples' thickness and the thickness dependence is the result of at least two mechanisms: the first is the CISS effect, and the second reduces the spin polarization due to scattering. Temperature dependence studies provide the first support for theoretical work that suggested that phonons may contribute to the spin polarization.

Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling.

The correlation between molecular structure and mechanism of supramolecular polymerizations is a topic of great interest, with a special focus on the pathway complexity of porphyrin assemblies. Their cooperative polymerization typically yields highly ordered, long 1D polymers and is driven by a combination of π-stacking due to solvophobic effects and hydrogen bonding interactions. Subtle changes in molecular structure, however, have significant influence on the cooperativity factor and yield different aggregate types (J- versus H-aggregates) of different lengths. In this study, the influence of amide connectivity on the self-assembly behavior of porphyrin-based supramolecular monomers was investigated. While in nonpolar solvents, C=O centered monomers readily assemble into helical supramolecular polymers via a cooperative mechanism, their NH centered counterparts form short, non-helical J-type aggregates via an isodesmic pathway. A combination of spectroscopy and density functional theory modelling sheds light on the molecular origins causing this stunning difference in assembly properties and demonstrates the importance of molecular connectivity in the design of supramolecular systems. Finally, their mutual interference in copolymerization experiments is presented.

Pasteur and chirality: A story of how serendipity favors the prepared minds.

During the XIXth century, France has been the theater of many discoveries in stereochemistry thanks to prestigious physicists, chemists, and crystallographers. Among them, Louis Pasteur is certainly the father of molecular chirality (the so-called molecular dissymmetry), and because of the exceptionally favored conditions of his famous discovery on the resolution of tartrates, his findings have often been attributed to serendipity. But let us not forget that "in the fields of observation, chance only favors the prepared minds."

Photodynamic Control of the Chain Length in Supramolecular Polymers: Switching an Intercalator into a Chain Capper.

Supramolecular systems are intrinsically dynamic and sensitive to changes in molecular structure and external conditions. Because of these unique properties, strategies to control polymer length, composition, comonomer sequence, and morphology have to be developed for sufficient control over supramolecular copolymerizations. We designed photoresponsive, mono acyl hydrazone functionalized benzene-1,3,5-tricarboxamide (m-BTA) monomers that play a dual role in the coassembly with achiral alkyl BTAs (a-BTA). In the E isomer form, the chiral m-BTA monomers intercalate into stacks of a-BTA and dictate the chirality of the helices. Photoisomerization to the Z isomer transforms the intercalator into a chain capper, allowing dynamic shortening of chain length in the supramolecular aggregates. We combine optical spectroscopy and light-scattering experiments with theoretical modeling to show the reversible decrease in length when switching from the E to Z isomer of m-BTA in the copolymer with inert a-BTA. With a mass-balance thermodynamic model, we gain additional insights into the composition of copolymers and length distributions of the species over a broad range of concentrations and mixing ratios of a-BTA/m-BTA. Moreover, the model was used to predict the impact of an additive (chain capper and intercalator) on the chain length over a range of concentrations, showing a remarkable amplification of efficiency at high concentrations. By employing a stimuli-responsive comonomer in a mostly inert polymer, we can cooperatively amplify the effect of the switching and obtain photocontrol of polymer length. Moreover, this dynamic decrease in chain length causes a macroscopic gel-to-sol phase transformation of the copolymer gel, although 99.4% of the organogel is inert to the light stimulus.