One-Step Syntheses of 3,4-Disubstituted Isochroman-1-ones by the Annulation of Benzoic Acids with Nitroalkenes.

The Rh(III)-catalyzed annulation of benzoic acids with nitroalkenes was disclosed to afford a wide range of 3,4-disubstituted isochroman-1-ones with excellent regioselectivity and high catalytic efficiency. Both aromatic and aliphatic nitroalkenes participated in this cyclization reaction successfully. The synthetic value of 3,4-disubstituted isochroman-1-ones was proven by a series of derivatizations. Furthermore, a reliable mechanism is outlined on the basis of experimental investigations and related precedents.

Self-Assembly of Amphiphilic Schiff Base and Selectively Turn on Circularly Polarized Luminescence by Al3.

We designed glutamide-derived amphiphilic Schiff bases containing three different aldehyde moieties for the fabrication of circularly polarized luminescence (CPL) emitting materials. Upon self-assembly in acetonitrile, Schiff bases featuring 4-(dimethylamino)-2-hydroxylbenzaldehyde and 1-hydroxy-2-naphthaldehyde groups form supramolecular gels with twist and fiber structures, respectively, whereas Schiff bases featuring 2-hydroxy-1-naphthaldehyde groups form precipitation with flake structures. Although emission and circular dichroism signals can be detected from the supramolecular gels formed by amphiphilic Schiff bases, none of them exhibits a circularly polarized luminescence (CPL). Although Mg2+, Zn2+, and Al3+ can significantly enhance the fluorescence of the Schiff bases, interestingly, only Al3+ ion is able to turn on the CPL emission. This study on the one hand provides a simple method for the fabrication of CPL-emitting supramolecular materials and on the other hand offers a novel way for the sensing of aluminum ion with supramolecular materials.

Circularly Polarized Luminescence from a Pyrene-Cyclodextrin Supra-Dendron.

Soft nanomaterials with circularly polarized luminescence (CPL) have been currently attracting great interest. Here, we report a pyrene-containing π-peptide dendron hydrogel, which shows 1D and 2D nanostructures with varied CPL activities. It was found that the individual dendrons formed hydrogels in a wide pH range (3-12) and self-assembled into helices with pH-tuned pitches. Through chirality transfer, the pyrene unit could show CPL originated from both the monomer and excimer bands. When cyclodextrin was introduced, different supra-dendrons were obtained with ß-cyclodextrin (PGAc@ß-CD) and γ-cyclodextrin (PGAc@γ-CD) through host-guest interactions, respectively. Interestingly, the PGAc@ß-CD and PGAc@γ-CD supra-dendrons self-assembled into 2D nanosheet and entangled nanofibers, respectively, showing cyclodextrin induced circularly polarized emission from both the monomer and excimer bands of the pyrene moiety. Thus, through a simple host-guest interaction, both the nanostructures and the chiroptical activities could be modulated.

Photoirradiation-generated radicals in two-component supramolecular gel for polymerization.

While supramolecular gels have been attracting great interest due to their easy design and fabrication, development of new applications based on these gels is always a challenging topic. Here, we report a two-component supramolecular gel that can generate and stabilize radicals through photo-irradiation, which can be subsequently used for polymerization. It has been found that the electrostatic interactions between a cationic amphiphile and anionic sulfonate could afford co-assembly into a two-component supramolecular gel. Upon photo-irradiation, the gel changed colour and produced the radicals, as verified from the EPR measurements. The radical thus formed in the supramolecular gel is relatively stable and could be used to polymerize acrylic acid directly without deoxygenation. In contrast, acrylic acid could not be polymerized in solution under the same conditions. This work expands the application scope of supramolecular gels.

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.

Solvent-polarity-tuned morphology and inversion of supramolecular chirality in a self-assembled pyridylpyrazole-linked glutamide derivative: nanofibers, nanotwists, nanotubes, and microtubes.

The self-assembly of a low-molecular-weight organogelator into various hierarchical structures has been achieved for a pyridylpyrazole linked L-glutamide amphiphile in different solvents. Upon gel formation, supramolecular chirality was observed, which exhibited an obvious dependence on the polarity of the solvent. Positive supramolecular chirality was obtained in nonpolar solvents, whereas it was inverted into negative supramolecular chirality in polar solvents. Moreover, the gelator molecules self-assembled into a diverse array of nanostructures over a wide scale range, from nanofibers to nanotubes and microtubes, depending on the solvent polarity. Such morphological changes could even occur for the xerogels in the solvent vapors. We found that the interactions between the pyridylpyrazole headgroups and the solvents could subtly change the stacking of the molecules and, hence, their self-assembled nanostructures. This work exemplifies that organic solvents can significantly involve the gelation, as well as tune the structure and properties, of a gel.

A dual-functional metallogel of amphiphilic copper(II) quinolinol: redox responsiveness and enantioselectivity.

A dual-functional metallogel, which was based on the copper(II) complex of quinolinol-substituted L-glutamide, showed both redox-responsive and enantioselective properties; moreover, the metallogels collapsed into a sol after reduction and could be revived upon subsequent oxidation. The supramolecular chirality and morphology also reversible changed with the gel-sol transition. Furthermore, the metallogels showed new enantioselective recognition towards chiral aromatic amino acids. A new emission band in the blue-light region at around 393 nm appeared when the metallogels encountered L-aromatic amino acids, whereas no new emission band was observed for the corresponding D-aromatic amino acids. Such enantioselectivity only occurred in the gel state. No similar phenomenon could be observed in solution. This result suggested that, during the gel formation, the gelator molecules self-assembled into ordered, chiral supramolecular structures and enhanced the enantiorecognition of the L-aromatic amino acids.

Supramolecular assemblies of amphiphilic L-proline regulated by compressed CO2 as a recyclable organocatalyst for the asymmetric aldol reaction.

Compressed CO2 triggers the formation of amphiphilic proline supramolecular assemblies in water, which catalyze the asymmetric aldol reaction without any additives. Compressed CO2 can dynamically regulate the size of the assemblies and subsequently the catalyst activity and selectivity. Furthermore, CO2 provides the merit of easy separation and purification, making the process sustainable and recyclable.

Amphiphilic Schiff base organogels: metal-ion-mediated chiral twists and chiral recognition.

New amphiphilic gelators that contained both Schiff base and L-glutamide moieties, abbreviated as o-SLG and p-SLG, were synthesized and their self-assembly in various organic solvents in the absence and presence of metal ions was investigated. Gelation test revealed that o-SLG formed a thermotropic gel in many organic solvents, whilst p-SLG did not. When metal ions, such as Cu(2+), Zn(2+), Mg(2+), Ni(2+), were added, different behaviors were observed. The addition of Cu(2+) induced p-SLG to from an organogel. In the case of o-SLG, the addition of Cu(2+) and Mg(2+) ions maintained the gelating ability of the compound, whilst Zn(2+) and Ni(2+) ions destroyed the gel. In addition, the introduction of Cu(2+) ions caused the nanofiber gel to perform a chiral twist, whilst the Mg(2+) ions enhanced the fluorescence of the gel. More interestingly, the Mg(2+)-ion-mediated organogel showed differences in the fluorescence quenching by D- and L-tartaric acid, thus showing a chiral recognition ability.

Self-assembly of copper(II) ion-mediated nanotube and its supramolecular chiral catalytic behavior.

Self-assembly of several low-molecular-weight L-glutamic acid-based gelators, which individually formed helical nanotube or nanofiber structures, was investigated in the presence of Cu(2+) ion. It was found that, when Cu(2+) was added into the system, the self-assembly manner changed significantly. Only in the case of bolaamphiphilic glutamic acid, N,N'-hexadecanedioyl-di-L-glutamic acid (L-HDGA), were the hydrogel formation as well as the nanotube structures maintained. The addition of Cu(2+) ion caused a transition from monolayer nanotube of L-HDGA to a multilayer nanotube with the thickness of the tubular wall about 10 nm. For the other amphiphiles, the gel was destroyed and nanofiber structures were mainly formed. The formed Cu(2+)-containing nanostructures can function as an asymmetric catalyst for Diels-Alder cycloaddition between cyclopentadiene and aza-chalcone. In comparison with the other Cu(2+)-containing nanostructures, the Cu(2+)-mediated nanotube structure showed not only accelerated reaction rate, but enhanced enantiomeric selectivity. It was suggested that, through the Cu(2+) mediated nanotube formation, the substrate molecules could be anchored on the nanotube surfaces and produced a stereochemically favored alignment. When adducts reacted with the substrate, both the enantiomeric selectivity and the reaction rate were increased. Since the Cu(2+)-mediated nanotube can be fabricated easily and in large amount, the work opened a new way to perform efficient chiral catalysis through the supramolecular gel.

Circularly Polarized Luminescence of Aluminum Complexes for Chiral Sensing of Amino Acid and Amino Alcohol.

Determination of the absolute configuration (AC) of chiral molecules is a key issue in many fields related to chirality such as drug development, the asymmetric reaction screening, and the structure determination of natural compounds. Although various methods, such as X-ray crystallography and NMR spectroscopy, are used to determine the AC, a simple and cheap alternative method is always anticipated. So far, electronic circular dichroism (ECD) spectroscopy has been widely used to ascertain the AC and enantiomeric excess (ee) values by applying appropriate organic probes. Here, circularly polarized luminescence (CPL) spectroscopy was applied to determine the AC and ee values of a series of amino acid and amino alcohol. The measurements were conducted by mixing the amino acids or amino alcohols with an achiral 1-hydroxy-2-naphthaldehyde. Upon in situ formation of the Schiff base complexes, the system showed emission enhancement and CPL in the presence of Al3+ , whose intensity and sign can be used to assign the chiral sense of the amino acids and amino alcohols. The authenticity of the method was further compared with the established CD spectroscopy, revealing that CPL spectra of formed Al3+ complex were effective to determine the AC of chiral species.

Circularly polarized luminescence of achiral open-shell π-radicals.

Stable luminescent π-radicals with doublet emission have attracted growing attention for functional molecular materials. However, their chiroptical properties, particularly their doublet emission-based circularly polarized luminescence, have never been investigated. Here, we investigate the circularly polarized luminescence (CPL) properties of a series of achiral luminescent open-shell π-radicals through various chirality regulation approaches, including induction by a magnetic field, supramolecular coassembly and chiral liquid crystal encapsulation.

Enantioselective Recognition by Chiral Supramolecular Gels.

Chiral supramolecular gels, in which small organic molecules self-assemble into chiral nanostructures and entangle each other to immobilize solvents through various noncovalent interactions, can work as a matrix for enantioselective recognition on chiral analytes. Through gelation and the formation of well-defined nanostructures, the chiral sense of the component molecules can be accumulated or amplified, and thus, the enantioselective recognition ability can be enhanced. Furthermore, a chiral microenvironment formed in the gel networks could provide additional stereochemical recognition geometry and attribute to efficient recognition. In this focus review, enantioselective recognition on chiral analytes through chiral supramolecular gels, with either amplified signals or the gel-sol phase transition, is discussed. This review is expected to provide useful insights into the design and fabrication of supramolecular gel systems with chiral features and high enantioselectivity.

A Chiroptical Logic Circuit Based on Self-Assembled Soft Materials Containing Amphiphilic Spiropyran.

A chiral logic circuit is proposed based on the multiple chiroptical responsiveness of a supramolecular gel material. The gel is fabricated by mixing a chiral gelator and a spiropyran derivative. Chiral responsiveness including the chiral switch and the logic gate is realized through the combined chirality transfer, photochromism, and acidichromism of the system.

Enantioselective recognition of a fluorescence-labeled phenylalanine by self-assembled chiral nanostructures.

Self-assembled chiral nanostructures such as nanofibers and nanotubes formed by a pyridylpyrazole-conjugated l-glutamide showed an enantioselective recognition toward a fluorescence labeled chiral amino acid.

Water tuned the helical nanostructures and supramolecular chirality in organogels.

Water was found to tune the self-assembled nanostructures of a cationic amphiphile in organic solvents from nanofibers to helical tapes, helical tubes and chiral nanotwists with various pitch lengths depending on water content. Inversion of CD spectra was observed in the water-triggered polar and non-polar solvent gels.