Tunable molecular packing modes via H- or J-aggregates in the supramolecular helical nanostructures from an achiral C3 symmetric molecule.

The self-assembly of a C3-symmetric molecule benzene-1,3,5-tricarboxylate substituted with methyl cinnamate (BTECM) has been investigated by a reprecipitation method in H2O and cetyltrimethylammonium bromide (CTAB) aqueous solution, respectively. The nanostructures and characteristics of the assemblies were monitored by UV-Vis spectroscopy, fluorescence (FL) spectroscopy, circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that helical nanostructures were successfully assembled from the achiral C3 molecule BTECM. More importantly, the helices aggregated via different packing modes in H2O and CTAB aqueous solution. In H2O, the nanostructures underwent a process of particles, fibers and helices via H-type aggregate upon aging. In the case of CTAB aqueous solution (1.2 mM), the helices were translated from particles and the molecules were inclined to aggregate via the J-type mode. In addition, the aggregation process could be accelerated by raising the temperature proved by UV-Vis spectra. A molecular aggregation mechanism was proposed based on the experimental results.

Circularly Polarized Organic Room Temperature Phosphorescence from Amorphous Copolymers.

Organic optoelectronic functional materials featuring circularly polarized emission and persistent luminescence represent a novel research frontier and show promising applications in data encryption, displays, biological imaging, and so on. Herein, we present a simple and universal approach to achieve circularly polarized organic phosphorescence (CPP) from amorphous copolymers by the incorporation of axial chiral chromophores into polymer chains via radical cross-linked polymerization. Our experimental data reveal that copolymers (R/S)-PBNA exhibit a maximum CPP efficiency of 30.6% and the largest dissymmetric factor of 9.4 × 10-3 and copolymers (R/S)-PNA show the longest lifetime of 0.68 s under ambient conditions. Given the CPP property of these copolymers, their potential applications in multiple information encryption and displays are demonstrated, respectively. These findings not only lay the foundation for the development of amorphous polymers with superior CPP but also expand the outlook of room-temperature phosphorescent materials.

Self-Assembly of Hierarchical Chiral Nanostructures Based on Metal-Benzimidazole Interactions: Chiral Nanofibers, Nanotubes, and Microtubular Flowers.

Controlled hierarchical self-assembly of synthetic molecules into chiral nanoarchitectures to mimic those biological chiral structures is of great importance. Here, a low-molecular-weight organogelator containing a benzimidazole moiety conjugated with an amphiphilic l-glutamic amide has been designed and its self-assembly into various hierarchical chiral nanostructures is investigated. Upon gel formation in organic solvents, 1D chiral nanostructure such as nanofiber and nanotube are obtained depending on the solvents. In the presence of transition and rare earth metal ions, hierarchical chiral nanostructures are formed. Specifically, the addition of TbCl3 , EuCl3 , and AgNO3 leads to nanofiber structures, while the addition of Cu(NO3 )2 , Tb(NO3 )3 , or Eu(NO3 )3 provides the microflower structures and microtubular flower structures, respectively. While Eu(III) and Tb(III)-containing microtubular flowers keep the chirality, the Cu(II)-coordinated microflowers lose chirality. More interestingly, the nanofibers formed by the gelator coordinated with Eu(III) or Tb(III) ions show not only the supramolecular chirality but also the circularly polarized luminescence.

Symmetry Breaking in the Supramolecular Gels of an Achiral Gelator Exclusively Driven by π-π Stacking.

Supramolecular symmetry breaking, in which chiral assemblies with imbalanced right- and left-handedness emerge from achiral molecular building blocks, has been achieved in the organogels of a C3-symmetric molecule only via π-π stacking. Specifically, an achiral C3-symmetric benzene-1,3,5-tricarboxylate substituted with methyl cinnamate through ester bond was found to form organogels in various organic solvents. More interestingly, when gels formed in cyclohexane, symmetry breaking occurred; i.e., optically active organogels together with the helical nanofibers with predominant handedness were obtained. Furthermore, the stochastically appeared imbalanced helicity could be driven to desired handedness by utilizing slight chiral solvents such as (R)- or (S)-terpinen-4-ol. Remarkably, the handedness of supramolecular assemblies thus formed could be kept even when the chiral solvents were removed. For the first time, we show that symmetry breaking can occur in supramolecular gel system driven exclusively through π-π stacking.

Tuning the gelation ability of racemic mixture by melamine: enhanced mechanical rigidity and tunable nanoscale chirality.

Understanding the relationship between molecular chirality of the gelators and the properties of the assembled supramolecular gels could be very important for developing novel functional soft matters. Although mixing the enantiomers with different molar ratios has been proved to be useful for modulating supramolecular assemblies, usually the racemates of different chiral molecules are not good gelators. In this study, the coassembly of the glutamic acid-based bolaamphiphile racemate and melamine was found to form hydrogels, while the assembly of the racemate only produced precipitates. Remarkably, the racemic hydrogels show lower CGC value, enhanced mechanical rigidity, and dual pH-responsive ability compared to the pure enantiomer hydrogels. The gelation properties, nanoscale chirality, and nanostructures of the racemic hydrogels can be regulated flexibly by changing molar ratios of different molecular building blocks.

Macroscopic chirality of supramolecular gels formed from achiral tris(ethyl cinnamate) benzene-1,3,5-tricarboxamides.

A C3 -symmetric benzene-1,3,5-tricarboxamide substituted with ethyl cinnamate was found to self-assemble into supramolecular gels with macroscopic chirality in a DMF/H2 O mixture. The achiral compound simultaneously formed left- and right-handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester-amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.

Disassembly of spherical structures into nanohelices by good solvent dilution.

Supramolecular self-assembly of low molecular weight molecules into various organic nanostructures has attracted considerable research interest. However, preparing organic nanostructures through a top-down method, such as the disassembly of one large structure into many smaller nanoscale nanostructures, still remains a big challenge. Here, we make use of anti-solvent method to regulate the hierarchical self-assembly of an achiral C3-symmetric molecule in THF/water to prepare various nanostructures, including spherical structures, nanofibers, nanoribbons and nanotwists. Interestingly, the spherical structures could disassemble into nanohelices through good solvent dilution, providing a nanoscale top-down method to prepare organic nanostructures.

Asymmetric catalysis mediated by a mirror symmetry-broken helical nanoribbon.

Although chirality has been recognized as an essential entity for life, it still remains a big mystery how the homochirality in nature emerged in essential biomolecules. Certain achiral motifs are known to assemble into chiral nanostructures. In rare cases, their absolute geometries are enantiomerically biased by mirror symmetry breaking. Here we report the first example of asymmetric catalysis by using a mirror symmetry-broken helical nanoribbon as the ligand. We obtain this helical nanoribbon from a benzoic acid appended achiral benzene-1,3,5-tricarboxamide by its helical supramolecular assembly and employ it for the Cu2+-catalyzed Diels-Alder reaction. By thorough optimization of the reaction (conversion: > 99%, turnover number: ~90), the enantiomeric excess eventually reaches 46% (major/minor enantiomers = 73/27). We also confirm that the helical nanoribbon indeed carries helically twisted binding sites for Cu2+. Our achievement may provide the fundamental breakthrough for producing optically active molecules from a mixture of totally achiral motifs.

Chiral Nanoarchitectonics: Towards the Design, Self-Assembly, and Function of Nanoscale Chiral Twists and Helices.

Helical structures such as double helical DNA and the α-helical proteins found in biological systems are among the most beautiful natural structures. Chiral nanoarchitectonics, which is used here to describe the hierarchical formation and fabrication of chiral nanoarchitectures that can be observed by atomic force microscopy (AFM), scanning tunneling microscopy (STM), scanning electron microscopy (SEM), or transmission electron microscopy (TEM), is one of the most effective ways to mimic those natural chiral nanostructures. This article focuses on the formation, structure, and function of the most common chiral nanoarchitectures: nanoscale chiral twists and helices. The types of molecules that can be designed and how they can form hierarchical chiral nanoarchitectures are explored. In addition, new and unique functions such as amplified chiral sensing, chiral separation, biological effects, and circularly polarized luminescence associated with the chiral nanoarchitectures are discussed.

Strong circularly polarized luminescence from the supramolecular gels of an achiral gelator: tunable intensity and handedness.

Although the importance of circularly polarized luminescence (CPL) materials has been widely recognized, the CPL responses of supramolecular gels are still rarely studied. Moreover, developing CPL materials based on supramolecular gels is of great significance, due to their special advantages and important applications. Herein, we report the first circularly polarized supramolecular gels self-assembled exclusively from a simple achiral C3-symmetric molecule. Most importantly, the excellent tunability of these novel CPL materials, which benefits from achiral molecular building blocks as well as the nature of supramolecular gels, has been investigated. Thus, the CPL intensity of these supramolecular gels is easily enhanced by mechanical stirring or doping chiral amines. The handedness of CPL signals is controlled by the chirality of organic amines.

H-bond and π-π stacking directed self-assembly of two-component supramolecular nanotubes: tuning length, diameter and wall thickness.

A series of supramolecular nanotubes with fine-tuned length, diameter and wall thickness were obtained from co-assembly of an L-glutamic acid based bolaamphiphile (HDGA) and melamine with different molar ratios. The changes in tubular nanostructures were found to be dependent on different self-assembly mechanisms.

Sensitive and photo-triggered transformation of hierarchical helices assembled from achiral bolaamphiphiles.

Chiral nanostructures, normally formed by chiral molecules, play an essential role in natural systems. The helical assemblies constructed by achiral molecular building blocks are still rare and their regulating mechanisms have not been well studied. An achiral cinnamoyl-terminated bolaamphiphile with three methylene unit spacers was found to self-assemble into hierarchically helical nanostructure. The photo-triggered changes in a small number of achiral molecular building blocks would dramatically and reversibly lead to great variations in the helical nanostructures. Thus, the helical supramolecular assemblies can be altered through changing a very small number of achiral molecular building blocks. Moreover, the co-assembly of the achiral bolaamphiphiles with ds-DNA produced uniform left-handed helices, which were also changed upon slight photoirradiation.

Supramolecular copolymers obtained from two-component gels: metal ion-mediated cross-linking, enhanced viscoelasticity and supramolecular yarns.

The hydrogels based on the co-assembly of bolaamphiphilic L-histidine and 2,2'-bipyridine-dicarboxylic acids were transformed into viscoelastic supramolecular polymers by cross-linking with Cu(II) ions, and macroscopic supramolecular yarns were obtained by direct drawing from a dilute aqueous solution of the supramolecular polymers.