Supramolecular Helical Structure Research Articles

Room-Temperature Liquid Crystalline Tetraphenylethylene-Surfactant Complex with Chiral Supramolecular Structure and Tunable Circularly Polarized Luminescence.

A novel room-temperature liquid crystal of tetraphenylethylene derivative (TPE-DHAB) was synthesized using an ionic self-assembly strategy. The TPE-DHAB complex exhibits typical aggregation-induced emission properties and a unique helical supramolecular structure. Moreover, the generation and handedness inversion of circularly polarized luminescence (CPL) can be achieved through further chiral solvation, providing a facile approach to fabricate room-temperature liquid crystalline materials with controllable supramolecular structures and tunable CPL properties through a synergistic strategy of ionic self-assembly and chiral solvation process.

Flexible Anti‐Counterfeiting Circularly Polarized Luminescent Elastomer from Supramolecular Polyurethanes

AbstractSupramolecular polymers with circularly polarized luminescence (CPL) have promoted future intelligence development of polymer‐based materials for flexible display. However, preparing polymer‐based CPL materials with simultaneous enhanced luminescence dissymmetry factor (|glum|) and mechanical performance for industrial applications remains challenging. This work develops an eco‐friendly preparation method for preparing CPL elastomers from supramolecular polyurethanes bearing chiral fluorescent S (or R)‐1,1′‐Bi(2‐naphthol) (BINOL) groups in a solvent‐free system. Surprisingly, a polymer system containing 0.0028 mol% of chiral BINOL unit is sufficient to emit the significant CPL‐activity with a |glum| value of 2.30 × 10−2, appear a good mechanical toughness of 56.28 ± 3.9 MJ·m−3, thereby exhibit multiple flexible anti‐counterfeiting behaviors. The long‐range ordered microphase arrangement in polyurethanes is the key to improving both mechanical properties and |glum|. This is attributed to in‐situ additive polymerization of BINOL‐based isocyanate prepolymer and macromolecular polyols induced helical supramolecular structure, afforded solid‐state films with flexibility and chiral amplification. Furthermore, these results from Circular dichroism, CPL, Fourier transform infrared, X‐ray diffraction analyses, and atomic force microscope confirm the formation of long‐range ordered microphase arrangement through the synergistic effect of hydrogen bonding and π–π interactions. This work offers significant insights into the construction of CPL elastomers for developing novel flexible display materials.

Perovskite-Supramolecular Co-Assembly for Chiral Optoelectronics.

Hybrid inorganic-organic perovskites with chiral response and outstanding optoelectronic characteristics are promising materials for next-generation spin-optoelectronics. In particular, two-dimensional (2D) perovskites are promising chiroptical candidates due to their unique ability to incorporate chiral organic cations into their crystal structure, which imparts chirality. To enable their practical applications in chiral optoelectronic devices, it is essential to achieve an anisotropy factor (gCD ∼ 2) in chiral 2D perovskites. Currently, chiral 2D perovskites exhibit a relatively low gCD of 3.1 × 10-3. Several approaches have been explored to improve the chiral response of chiral 2D perovskites, including tailoring the molecular structure of chiral cations and increasing the degree of octahedral tilting in the perovskite lattice. However, current methods for chiral amplification have only achieved a moderate enhancement of gCD by 2-fold and are often accompanied by undesirable shifts or inversion in the circular dichroism spectra. There is a need for a more efficient approach to enhancing the chirality in 2D perovskites. Here, we report an innovative coassembly process that allows us to seamlessly grow chiral 2D perovskites on supramolecular helical structures. We discover that the interactions between perovskites and chiral supramolecular structures promote crystal lattice distortion in perovskites, which improves the chirality of 2D perovskites. Additionally, the obtained hierarchical coassembly can effectively harness the structural chirality of the supramolecular helices. The multilevel chiral enhancement leads to an enhancement in gCD by 2.7-fold without compromising the circular dichroism spectra of 2D perovskites.

Preparation and temperature-controlled morphology of helical microrods composed of supramolecular α-cyclodextrin assemblies.

Significant efforts have been devoted so far to artificially fabricate supramolecular helical nano- and microstructures through the regulated assembly of biological and synthetic building blocks. However, the preparation of supramolecular helical structures with a regulated morphology remains challenging. Here, helical microrods composed of supramolecular α-cyclodextrin (α-CD) assemblies were fabricated by allowing an α-CD/1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)/2-pentanol mixture to stand at 30-60 °C under high humidity conditions. The morphology could be controlled by temperature to produce helical microrods with a regulated pitch and length. These helical rods can be applied as optical devices, chiral separation devices and asymmetric catalysts.

Supramolecular Helical Polymer Formed Via Complementary Dimerization of Bisporphyrin Cleft

We have been developing supramolecular polymers directed by unique host-guest motifs.1,2 During study, a tetrakisporphyrin monomer was discovered to form the supramolecular helical polymers.3,4 A lack of chirality resulted in the racemic mixture of the supramolecular helical polymers. In this presentation, we report that the chirally-twisted pseudo macrocyclic tetrakisporphyrin monomer is self-assembled to form the one-handed helical supramolecular structures. Two amino acid side chains were installed at the termini of a tetrakisporphyrin monomer. The intramolecular antiparallel hydrogen bonding between the amino acid side chains resulted in the pseudo macrocyclic conformation, which was chirally-twisted. The right-handed and left-handed conformations of the pseudo macrocyclic monomer are determined by the absolute configuration of the stereogenic centers. The chirally-twisted pseudo macrocyclic monomer was self-assembled to result in the one-handed helical structures with very high association constants. The well-developed supramolecular chains generated entangled polymer solution, which suggests the formation of the well-developed long supramolecular polymer chains. Atomic force microscopy visualized the long supramolecular polymer chains with the length more than 100 nm. The right-handed helical morphology was formed from the D-amino acid side chains.

Structural transition in a ferroelectric nano-dispersed cholesteric liquid crystal

ABSTRACT We present a theoretical study of the orientational and electrical behaviors of a cholesteric liquid crystal dispersed with ferroelectric nanoparticles. We assume a soft planar coupling between the liquid crystal molecules and the nanoparticles. We consider two spiral structures in the ferroelectric nano-dispersed system under an external electric field. This assumption is due to the fact that the director and the polarization vector would have different pitches of spiral structure. We study the behavior of the average polarization and the pitch of the helical structure as a function of the field strength. The impact of ferroelectric nanoparticles on cholesteric-nematic phase transition is investigated by calculating the critical electric field. The influence of field strength and material parameters on the phase transition is also discussed. The calculations are based on a developed continuum theory and a modified form of free energy for the helical supramolecular structure. The influence of nanoparticle volume fraction on the helix unwinding of both spiral structures is studied. It is found that an electric field with a sufficiently high strength causes an increase in the pitch of the helical structure of polarization. We obtain a critical volume fraction of nanoparticles, after which the pitch of the polarization helical structure differs from the director pitch.

Helical micelle of an achiral surfactant from the template interaction with dendrimer

The electrostatic interaction between of poly(amidoamine) (PAMAM) G9 dendrimer and an achiral surfactant, dodecylbenzenesulfonic acid (DBSA), leads to the formation of nucleosome-like structure, where the globular dendrimer molecule directs the DBSA cylindrical micelle to wrap around it spirally with a regular pitch length of 3.2 ∼ 4.3 nm. Molecular dynamics simulation demonstrates that the spherical micelles of DBSA in the aqueous solution first condense on the dendrimer surface via the electrostatic attraction. The micelles then merge with their neighbors to form cylinders bending around the dendrimer, which further connect with one another to form a spring-like helix wrapping around the dendrimer. The discovery of the helical supramolecular structure attests the universality of soft cylindrical building block such as DNA and micelle to twist and wrap helically around the oppositely charged particle such as histone protein and dendrimer for attaining the optimal charge matching at the expense of the bending energy of the cylinder.

Colorful patterned polyacrylate films prepared using cholesteric liquid-crystalline mixtures with a smectic order

ABSTRACT Polymer-stabilised cholesteric liquid crystal (PSCLC) films with selective circularly polarised light reflection have attracted much attention for their applications as polarisers, energy-saving windows and for displays. Herein, CLC mixtures were prepared using a nematic LC LC242 and a chiral compound S-6 with enantiotropic SmA and SmC* phases, which exhibited a cholesteric phase with a smectic order. After photopolymerisation, the PSCLC films with fingerprint structure at the surfaces and supramolecular helical structure inside were obtained. Due to the existence of short-range smectic order in the cholesteric structure, the Bragg reflection bands were broadened. For a CLC mixture, with increasing temperature, the short-range smectic order was suppressed, and the selective Bragg reflection band shifted to the short wavelength. Based on this thermochromic behaviour, colourful PSCLC patterns and gratings were prepared, which were able to be applied in decoration and anti-counterfeiting. Since the PSCLC films can be obtained within several seconds under air, large-area films can be prepared on coating lines at low-cost.

Improving the solubility of tetrahydropalmatine by introducing sulfonic acid by forming pharmaceutical salts of tetrahydropalmatine with supramolecular helical structure via CAHBs

Improving the solubility of tetrahydropalmatine by introducing sulfonic acid by forming pharmaceutical salts of tetrahydropalmatine with supramolecular helical structure via CAHBs

Engineering supramolecular helical assemblies via interplay between carbon(sp) tetrel and halogen bonding interactions.

Building supramolecular helical structures is a challenge due to difficulties in the design and control of competitive noncovalent forces. Herein, we report three scaffolds (1a, 1b, and 1c) decorated with -CN and -Br groups. These groups known for their ability to form multiple noncovalent interactions and with efficient design can be utilized to achieve such complex structures. X-Ray analyses revealed that the crystal packing of 1a, 1b and 1c is dominated by highly directional Br⋯CN Csp-tetrel bonding (1a), Br⋯π, Br⋯N (1b) and Br⋯Br (1c) XB interactions, and these interactions have led to the formation of achiral P/M, chiral M and achiral P/M helical assemblies, respectively. A detailed structural and computational analysis was performed to clarify the nature and estimate the strength of these interactions in helical assemblies. MEP analyses of 1a, 1b, and 1c have shown that the potential of electron-deficient and electron-rich regions within the structures has similar values. Yet, the geometric accessibility of σ-holes has differed with each scaffold. Thus, dominant interactions have changed and consequently led to different helical assembly formations. The interaction energies are around -11.4 (1a), -4.0 (1b), and -4.6 (1c) kcal mol-1 and mainly driven by dispersion, followed by electrostatic interactions. To our surprise, the Csp-tetrel bonding (1a), considered the weakest among non-covalent interactions, is the strongest interaction among the three scaffolds, which shows the importance of accessibility of Sigma holes. These findings are expected to contribute to the future rational design of complex self-assembled materials, utilizing Csp-tetrel and XB interactions, in various applications such as crystal engineering, organic semiconductors, sensor devices, and medicinal chemistry.

Heteroatom-directed supramolecular helical-rich architectures in N-terminal protected pyridyl aromatic amino acids

Supramolecular helical structures formed by the assembly of biological and bio-inspired building blocks (typically amino acids and peptides) are an exciting class of materials with prospective applications in biomedical technologies and electronics.

Metal-Enhanced Helical Chirality of Coil Macromolecules: Bioinspired by Metal Coordination-Induced Protein Folding

Although the supramolecular helical structures of biomacromolecules have been studied, the examples of supramolecular systems that are assembled using coils to form helical polymer chains are still limited. Inspired by enhanced helical chirality at the supramolecular level in metal coordination-induced protein folding, a series of alanine-based coil copolymers (poly-(l-co-d)-ala-NH2) carrying (l)- and (d)-alanine pendants were synthesized as a fresh research model to study the cooperative processes between homochirality property and metal coordination. The complexes of poly-(l-co-d)-ala-NH2 and metal ions underwent a coil-to-helix transition and exhibited remarkable nonlinear effects based on the enantiomeric excess of the monomer unit in the copolymers, affording enhanced helical chirality compared to poly-(l-co-d)-ala-NH2. More importantly, the synergistic effect of amplification of asymmetry and metal coordination triggered the formation of a helical molecular orbital on the polymer backbone via the coordination with the d orbital of copper ions. Thus, the helical chirality enhancement degree of poly-(l-co-d)-ala-NH2/Cu2+ complexes (31.4) is approximately 3 times higher than that of poly-(l-co-d)-ala-NH2/Ag+ complexes (9.8). This study not only provides important mechanistic insights into the enhancement of helical chirality for self-assembly but also establishes a new strategy for studying the homochiral amplification of asymmetry in biological supramolecular systems.

Structural and Thermodynamic Control of Supramolecular Polymers and DNA Assemblies with Cyanuric Acid: Influence of Substituents and Intermolecular Interactions.

Understanding the interactions and thermodynamic parameters that govern the structure and stability of supramolecular polymers is challenging because of their flexible nature and high sensitivity to weak intermolecular interactions. The application of both experimental and computational analyses reveals the role that substituents on cyanuric acid (Cy), and other nitrogen-containing heterocycles, play in the formation of novel helical supramolecular structures. In this report, we focus on how noncovalent interactions, including steric and stacking interactions, modulate the structural and physical properties of these assemblies. In-depth analyses and several examples of critical steric and electrostatic effects provide insight into the relationship between intermolecular interactions of Cy with nucleic acids and the structure and thermodynamic stability of the supramolecular polymers they form.

Colorfully Patterned Epoxy Resin Films with a Cholesteric Structure Prepared through a Photopolymerization Approach

Structurally colored epoxy resin films were prepared using a liquid crystalline (LC) epoxy monomer of E11M and a chiral additive of CA-iso through a photopolymerization approach. With the addition of the co-photoinitiator isopropyl thioxanthone and comonomer 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, the polymerization rate was increased. Since the epoxy resin films can be obtained within several seconds, they are feasible for large-area preparation on the coating line. The reflective wavelength was tunable by changing the concentration of CA-iso in the LC mixture. Diffuse-reflectance circular dichroism spectra indicated a right-handed helical supramolecular structure. Field-emission scanning electron microscopy images indicated a multilayer structure. Since the LC mixtures were thermochromic, colorfully patterned epoxy resin films were prepared by controlling the polymerization temperature. Moreover, LC gratings were also prepared, which were expected to be applied for anticounterfeiting.

Tetraphenylpyrene–Surfactant Complex with a Helical Supramolecular Structure and Circularly Polarized Luminescence

Tetraphenylpyrene–Surfactant Complex with a Helical Supramolecular Structure and Circularly Polarized Luminescence

One-Dimensional Helical Nanostructures from the Hierarchical Self-Assembly of an Achiral "Rod-Coil" Alternating Copolymer.

The self-assembly of alternating copolymers (ACPs) has attracted considerable interest due to their unique alternating nature. However, compared with block copolymers, their self-assembly behavior remains much less explored and their reported self-assembled structures are limited. Here, the formation of supramolecular helical structures by the self-assembly of an achiral rod-coil alternating copolymer named as poly(quarter(3-hexylthiophene)-alt-poly(ethylene glycol)) (P(Q3HT-alt-PEG)), is reported. The copolymer exhibits an interesting hierarchical self-assembly process, driven by the π-π stacking of the Q3HT segments and the solvophobic interaction of the alkyl chains in tetrahydrofuran (THF)-isopropanol mixed solvents. The copolymer first self-assembled into thin nanobelts with a uniform size, then grows to helical nanoribbons and eventually twisted into helical nanowires with an average diameter of 25 ± 9nm and a mean pitch of 80 ± 10nm. Dissipative particle dynamics (DPD) simulation supports the formation course of the helical nanowires. Furthermore, the addition of (S)-ethyl lactate and (R)-ethyl lactate in the self-assembly of P(Q3HT-alt-PEG) results in the formation of left-handed and right-handed chiral nanowires, respectively, demonstrating the tunability of the chirality of the helical wires. This study expands the library of ordered self-assembled structures of ACPs, and also brings a new strategy and mechanism to construct helical supramolecular structures.

Chiral Self-Recognition and Self-Discrimination Processes in Different Subphthalocyanine Aggregation Regimes

We have recently shown that, as a result of its rigid cone-shaped structure, racemic SubPcs trisubstituted with peripheral amides can self-assemble in two distinct regimes as a function of the solvent environment.1 In toluene, an apolar aromatic medium that can efficiently solvate p-surfaces, such compounds associate as tail-to-tail dimers (regime A). In methylcyclohexane (MCH), in contrast, they undergo a cooperative supramolecular polymerization process to yield non-centrosymmetric head-to-tail columnar stacks (regime B).2 SubPcs, being intrinsically chiral molecule, constitutes an ideal probe to study chiral self-sorting processes, which is the objective of this work. As depicted in the figure below, a racemic mixture of a trisubstituted SubPc can in principle self-assemble into different species. Homochiral dimers/polymers may form through a chiral self-recognition process: each enantiomer has a preference to aggregate with itself leading to helical supramolecular structures with a preferred handedness. At the other extreme, heterochiral dimers/polymers would be instead formed via a chiral self-discrimination process, where each enantiomer prefers to associate with the other, yielding purely racemic dimers/polymers displaying no predilection for a given helical sense. As an intermediate case, the enantiomers might show no strong self-sorting preference and yield statistical dimers/polymers.[1] C. G. Claessens, D. González-Rodríguez, M. S. Rodríguez-Morgade, A. Medina, T. Torres, Chem. Rev. 2014, 114, 2192.[2] (a) J. Calbo, J. Aragó, P. M. Viruela, E. Ortí, T. Torres, D. González-Rodríguez, Angew. Chem. Int. Ed. 2015, 54, 2543; (b) M. J. Mayoral, J. Guilleme, J. Calbo, J. Aragó, F. Aparicio, E. Ortí, T. Torres, D. González-Rodríguez, J. Am. Chem. Soc. 2020 , 142, 21017. Figure 1

Molecular Self-Assembly as a Trigger of Life Origin and Development.

The origin and reason for the homochirality of living cells go with the problem of a relatively narrow spectrum of the actual biological monomers compared to the whole theoretically possible spectrum of amino acids or carbohydrates. A limited number of bio-monomers implies some special feature differing from all other similar molecules that are not present in the living cell. Here we propose one of the candidates for such a peculiarity: the ability to form highly elongated helical supramolecular structures(strings) when precipitating from homochiral solutions. The strings' forming can be accompanied by spontaneous splitting and/or chiral purification of the initially racemic mixture. Our previous theoretical reasoning was based mainly on the biomimetic systems, while now we describe the strings forming in homochiral amino acid solutions.

Mutual Monomer Orientation To Bias the Supramolecular Polymerization of [6]Helicenes and the Resulting Circularly Polarized Light and Spin Filtering Properties.

We report on the synthesis and self-assembly of 2,15- and 4,13-disubstituted carbo[6]helicenes 1 and 2 bearing 3,4,5-tridodecyloxybenzamide groups. The self-assembly of these [6]helicenes is strongly influenced by the substitution pattern in the helicene core that affects the mutual orientation of the monomeric units in the aggregated form. Thus, the 2,15-substituted derivative 1 undergoes an isodesmic supramolecular polymerization forming globular nanoparticles that maintain circularly polarized light (CPL) with glum values as high as 2 × 10–2. Unlike carbo[6]helicene 1, the 4,13-substituted derivative 2 follows a cooperative mechanism generating helical one-dimensional fibers. As a result of this helical organization, [6]helicene 2 exhibits a unique modification in its ECD spectral pattern showing sign inversion at low energy, accompanied by a sign change of the CPL with glum values of 1.2 × 10–3, thus unveiling an example of CPL inversion upon supramolecular polymerization. These helical supramolecular structures with high chiroptical activity, when deposited on conductive surfaces, revealed highly efficient electron-spin filtering abilities, with electron spin polarizations up to 80% for 1 and 60% for 2, as measured by magnetic conducting atomic force microscopy.

Supramolecular Helical Assemblies of Dirhodium(II) Paddlewheels with 1,4-Diazabicyclo[2.2.2]octane: A Remarkable Substituent Effect on the Helical Sense Preference and Amplification of the Helical Handedness Excess of Metallo-Supramolecular Helical Polymers.

We report unique coordination-driven supramolecular helical assemblies of a series of dirhodium(II) tetracarboxylate paddlewheels bearing chiral phenyl- or methyl-substituted amide-bound m-terphenyl residues with triethylene glycol monomethyl ether (TEG) or n-dodecyl tails through a 1:1 complexation with 1,4-diazabicyclo[2.2.2]octane (DABCO). The chiral dirhodium complexes with DABCO in CHCl3/n-hexane (1:1) form one-handed helical coordination polymers with a controlled propeller chirality at the m-terphenyl groups, which are stabilized by intermolecular hydrogen-bonding networks between the adjacent amide groups at the periphery mainly via a cooperative nucleation-elongation mechanism as supported by circular dichroism (CD), vibrational CD, and variable-temperature (VT) absorption and CD analyses. The VT visible-absorption titrations revealed the temperature-dependent changes in the degree of polymerization. The columnar supramolecular helical structures were elucidated by X-ray diffraction and atomic force microscopy. The helix sense of the homopolymer carrying the bulky phenyl and n-dodecyl substituents is opposite those of other chiral homopolymers despite having the same absolute configuration at the pendants. A remarkably strong "sergeants and soldiers" (S&S) effect was observed in most of the chiral/achiral copolymers, while the copolymers of the bulky chiral phenyl-substituted dirhodium complexes with n-dodecyl chains displayed an "abnormal" S&S effect accompanied by an inversion of the helix sense, which could be switched to a "normal" S&S effect by changing the solvent composition. A nonracemic dirhodium complex of 20% enantiomeric excess bearing the less bulky chiral methyl substituents with n-dodecyl chains assembled with DABCO to form an almost one-handed helix (the "majority rule" (MR) effect), whereas the three other nonracemic copolymers showed a weak MR effect.