Chiral Pendant Research Articles

Hypervalent Iodine (III)-Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch.

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge-assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion as biaxial halogen bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial halogen bonding enables chiroptical evolution in solution, allowing for rational control over supramolecular chirality. Leveraging their strong binding affinity, the halogen bonding complexes manifested amorphous properties and deep eutectic behavior in the solid state. Capitalizing on these attributes, this work achieves the successful preparation of supramolecular glasses and deep eutectic solvents. Additionally, halogen bonding appended light irradiation-triggered luminescence through a hydrogen atom transfer process, showing applications in anti-counterfeit and display.

Structural Basis of Cucurbituril-Containing Self-Assembled Supramolecular Chiral Materials.

Macrocycle-based host-guest complexation offers an intriguing protocol in producing chiroptical materials, while the bulky size and dynamic exchange between hosts and guests hinders the ordered aggregation to afford the long-range chiral arrangement. It remains great challenges in assembling cucurbit[n]urils (CB[n]s) included complexes to induce supramolecular chirality ascribed to the excellent water solubility and flexible packing. Herein, we unveiled the structural basis on the formation of chiroptical coassemblies from CB[n] (n=6, 7) complexes. Perylene diimides (PDIs) with cationic chiral pendants formed complexes in the aqueous media, which selectively showed chiroptical properties. Chlorination at the bay position, increasing alkyl length of cationic chiral pendants or reducing the number of polyaromatic rings would hinder the chiral aggregation. In a comprehensive manner, CB[6] favors ordered aggregation into one-dimensional fibrous nanoarchitectures that greatly facilitates the supramolecular chirality. In contrast, CB[7] with larger cavity and water solubility shrinks the ordered arrangement of complexes, reducing the formation possibility of supramolecular chiral nanoarchitectures. This work suggests the great potential of CB[6] in the preparation and manipulation of supramolecular chiral assemblies, shedding light on the macrocycle-based functional chiroptical materials.

Structural Basis of Cucurbituril‐Containing Self‐Assembled Supramolecular Chiral Materials

Macrocycle‐based host‐guest complexation offers an intriguing protocol in producing chiroptical materials, while the bulky size and dynamic exchange between hosts and guests hinders the ordered aggregation to afford the long‐range chiral arrangement. It remains great challenges in assembling cucurbit[n]urils (CB[n]s) included complexes to induce supramolecular chirality ascribed to the excellent water solubility and flexible packing. Herein, we unveiled the structural basis on the formation of chiroptical coassemblies from CB[n] (n = 6, 7) complexes. Perylene diimides (PDIs) with cationic chiral pendants formed complexes in the aqueous media, which selectively showed chiroptical properties. Chlorination at the bay position, increasing alkyl length of cationic chiral pendants or reducing the number of polyaromatic rings would hinder the chiral aggregation. In a comprehensive manner, CB[6] favors ordered aggregation into one‐dimensional fibrous nanoarchitectures that greatly facilitates the supramolecular chirality. In contrast, CB[7] with larger cavity and water solubility shrinks the ordered arrangement of complexes, reducing the formation possibility of supramolecular chiral nanoarchitectures. This work suggests the great potential of CB[6] in the preparation and manipulation of supramolecular chiral assemblies, shedding light on the macrocycle‐based functional chiroptical materials.

Size Control of Chiral Nanospheres Obtained via Nanoprecipitation of Helical Poly(phenylacetylene)s in the Absence of Surfactants.

Nanostructuration of dynamic helical polymers such as poly(phenylacetylene)s (PPAs) depends on the secondary structure adopted by the polymer and the functional group used to connect the chiral pendant to the PPA backbone. Thus, while PPAs with dynamic and flexible scaffolds (para- and meta-substituted, ω1<165°) generate by nanoprecipitation low polydisperse nanospheres with controllable size at different acetone/water mixtures, those with a quasi-static behavior and the presence of an extended, almost planar structure (ortho-substituted, ω1>165°), aggregate into a mixture of spherical and oval nanostructures whose size is not controlled. Photostability studies show that poly(phenylacetylene) particles are more stable to light irradiation than when dissolved macromolecularly. Moreover, the photostability of the particle depends on the secondary structure of the PPA and its screw sense excess. This fact, in combination with the encapsulation ability of these polymer particles, allows the creation of light stimuli-responsive nanocarriers, whose cargo can be delivered by light irradiation.

Size Control of Chiral Nanospheres Obtained via Nanoprecipitation of Helical Poly(phenylacetylene)s in the Absence of Surfactants

AbstractNanostructuration of dynamic helical polymers such as poly(phenylacetylene)s (PPAs) depends on the secondary structure adopted by the polymer and the functional group used to connect the chiral pendant to the PPA backbone. Thus, while PPAs with dynamic and flexible scaffolds (para‐ and meta‐substituted, ω1&lt;165°) generate by nanoprecipitation low polydisperse nanospheres with controllable size at different acetone/water mixtures, those with a quasi‐static behavior and the presence of an extended, almost planar structure (ortho‐substituted, ω1&gt;165°), aggregate into a mixture of spherical and oval nanostructures whose size is not controlled. Photostability studies show that poly(phenylacetylene) particles are more stable to light irradiation than when dissolved macromolecularly. Moreover, the photostability of the particle depends on the secondary structure of the PPA and its screw sense excess. This fact, in combination with the encapsulation ability of these polymer particles, allows the creation of light stimuli‐responsive nanocarriers, whose cargo can be delivered by light irradiation.

Effect of length and functionality of the linker between the main chain and the chiral pendant on the helical nature of chiral poly(ionic liquids)

Chain length and the functionality of the linker between a chiral pendant and the main chain in vinylic chiral polymers play a crucial role in achieving their “helical sense”.

Chiral B-N AIEgens: Intense Blue Circularly Polarized Luminescence and Piezochromism.

We present a new class of blue circularly polarized luminescent emitters based on tetraarylaminoborane (TAAB) with considerable dissymmetry factor in the solid state. The chiral pendant 1-phenylethylamine in BN-RR and BN-SS imparts chirality to the core chromophore, resulting in circularly polarized luminescence signals (glum = 0.8 × 10-3) with a quantum yield of 33% in the crystalline state. This novel set of compounds also showcases intriguing thermally reversible piezochromism.

Effect of amino acid pendant groups on the helical configuration of polyphenylacetylene

In this study, several polyphenylacetylenes (PPAs) derivatives containing amino acid pendant groups were synthesized using a rhodium system catalyst (Rh(nbd)BPh4). The synthesized derivatives of PPAs included single chiral PPA with a single chiral center in the pendant groups and double chiral PPA' with two chiral centers in the pendant groups. The PPA and PPA' showed strong circular dichroism (CD) signals in the main chain absorption region of the UV-vis spectrum, while the monomer showed no CD signals. Furthermore, the PPA and PPA' with different chiral pendant groups showed different Cotton effects in the CD spectra. The results showed that these polymers existed in helical conformation, and the chiral center of the pendant groups affected the polymerization and helical structure of PPAs.

Supramolecular axial chirality in [N-I-N]+-type halogen bonded dimers.

Axial chiral molecules are extensively used as skeletons in ligands for asymmetric catalysis and as building blocks of chiroptical materials. Designing axial chirality at the supramolecular level potentially endows a material with dynamic tunability and adaptivity. In this work, for the first time, we have reported a series of halogen-bonded dimeric complexes with axial chirality that were formed by noncovalent bonds. The [N-I-N]+-type halogen bond is highly directional and freely rotatable with good linearity and ultra-high bond energy; this bond was introduced to couple quinoline moieties with chiral substitutes. The resultant dimers were stable in solutions with thermo-resistance. Prominent steric effects from the 2' chiral pendant allowed the chirality to be transferred to aryl skeletons with induced preferred axial chirality and optical activities. Halogen-bonded complexation presented visible emissions to afford luminescent axial chiral materials, whereby circularly polarized fluorescence and phosphorescence were achieved. The [N-I-N]+-type halogen bond performed as a powerful tool to construct functional axial chiral compounds, enriching the toolbox for asymmetric synthesis and optics.

Recent advances in helical polyacetylene derivatives used as coated chiral stationary phases for enantioseparation

The development of helical polyacetylene derivatives bearing different kinds of chiral pendants and the enantioseparation based on these helical polymers as coated CSPs for HPLC will be described.

Exploration of mandelic acid‐based polymethacrylates: Synthesis, properties, and stereochemical effects

AbstractMandelic acid (MA) was utilized as a chiral biomass‐based precursor to synthesize methacrylic monomers suitable for radical polymerization. A series of polymers were made that incorporated varying feeds of monomer stereopurity and the properties of these materials were investigated. High molar masses (&gt;90 kg/mol) were achieved and the chirality in each polymer closely reflected the stereopurity of the monomer feeds. It was discovered that stereochemical effects had very little influence on the thermal and viscoelastic properties of the polymers produced, however, the steric bulk of the chiral pendants resulted in glassy, amorphous, and thermally stable materials with very low degrees of entanglement. The synthesis, thermal, and viscoelastic properties are discussed.

Chiral Overpass Induction in Dynamic Helical Polymers Bearing Pendant Groups with Two Chiral Centers

AbstractThe dynamic behavior of helical polymers bearing pendant groups with two chiral centers was studied. Controlled conformational changes at the chiral units placed either closer to or further away from the main chain promote different helical structures. Although the first residue is usually responsible for determining a specific helicity (P or M), we now found that the second chiral center is also able to induce a preferred helical sense when it is located closer in space to the main chain, thereby cancelling the order from the first chiral moiety. This result was achieved through proper coordination with a metal cation. As proof of concept, poly(phenylacetylene)s (PPAs) that bear one and two chiral amino acid units of different sizes and configuration combinations (l/d‐alanine and l/d‐phenylalanine) as pendants were evaluated. In total, ten polymers were studied. This constitutes the first report of axial control from a remote stereocenter in polymers bearing complex chiral pendants.

Chiral information harvesting in helical poly(acetylene) derivatives using oligo(p-phenyleneethynylene)s as spacers.

A chiral harvesting transmission mechanism is described in poly(acetylene)s bearing oligo(p-phenyleneethynylene)s (OPEs) used as rigid achiral spacers and derivatized with chiral pendant groups. The chiral moieties induce a positive or negative tilting degree in the stacking of OPE units along the polymer structure, which is further harvested by the polyene backbone adopting either a P or M helix.

Highlighting spin selectivity properties of chiral electrode surfaces from redox potential modulation of an achiral probe under an applied magnetic field.

Impressive spin-related effects are observed in cyclic voltammetry (CV) experiments performed under an applied magnetic field on a non-ferromagnetic electrode modified with a thin electroactive oligothiophene film, either "inherently chiral" or featuring chiral pendants with stereogenic centres. When flipping the magnet's north/south orientation, the CV peaks of two achiral, chemically reversible Fe(iii)/Fe(ii) redox couples in aqueous or organic solution undergo impressive potential shifts (up to nearly 0.5 V depending on protocol conditions), specularly by changing the film's (R)- or (S)-configuration. The magnitude of the potential shift decreases upon increasing both the polymer film thickness and the distance between the permanent magnet and the electrode surface. Such unprecedented spin-related redox potential modulation, obtained in the absence of a magnetic electrode acting as a spin injector, provides striking evidence (as well as an attractive evaluation criterion) of the spin selectivity properties of chiral thin films.

Ferrocenes with simple chiral substituents: an in-depth theoretical and experimental VCD and ECD study.

Circular dichroism spectra in the IR range (VCD = vibrational circular dichroism) and in the UV range (ECD = electronic circular dichroism) have been recorded for both enantiomers of simple mono-substituted ferrocenes containing chiral pendants: 1-acetoxyethylferrocene, 1, 1-methoxyethylferrocene, 2, and 1-hydroxyethylferrocene, 3; the related disubstituted 1,1'-bis(1-hydroxyethyl)ferrocene, 4, was also considered. These two types of spectra, with the support of DFT calculations, concur to unequivocally confirm the absolute configuration for 1-4. In particular, our computational results point out the clear advantage of using an anharmonic oscillator model for the interpretation of VCD spectra of chiral ferrocenes. Interesting conformational properties are either confirmed or established by the technique, like the eclipsed conformation of the two cyclopentadienyl rings and an intra-molecular interaction involving the OH for 3. For 4, NMR, VCD and IR spectra are compatible with dimer formation and in this case a distorted conformation is predicted. Of utmost importance for the absolute configuration assignment in mono-substituted ferrocenes, we were able to identify a diagnostic VCD band at 950 cm-1 and a (low intensity) ECD band that clearly indicate the absolute configuration of the whole series.

Chiral-to-Chiral Communication in Polymers: A Unique Approach To Control Both Helical Sense and Chirality at the Periphery.

A novel approach to the classical Sergeants and Soldiers effect, using chiral Sergeants and chiral Soldiers, allows control over both helical and external chirality in helical polymers. In the systems reported here, it is possible to induce the same helical sense ( M or P) from either of the two enantiomers of a chiral pendant group ["chiral Soldier", major component; i.e., ( R)- or ( S)-1] when it faces a single enantiomer of an appropriate "chiral Sergeant" [minor component; i.e., ( S)-2]. For instance, the copolymer series poly[( R)-1 r- co-( S)-2(1- r)], poly[( S)-1 r- co-( S)-2(1- r)], and poly[( rac)-1 r- co-( S)-2(1- r)] adopt the same P helix even though the major component shows the opposite absolute configuration. This chiral-to-chiral communication effect is transmitted by the stabilization of different conformations in each enantiomeric form of the Soldier. As a result, this groundbreaking approximation to the Sergeants and Soldiers effect allows the preparation of a single-handed helix-which depends only on the Sergeant's configuration-with different chiralities on the helix periphery. Thus, a P helix can be decorated with the R isomer, S isomer, or even a racemic mixture of the chiral Soldier. A change in the absolute configuration of the Sergeant affords the opposite M helix, which can also be decorated with the R isomer, S isomer, or racemic mixture of the chiral Soldier.

Enantioselective Synthesis of 6,6-Disubstituted Pentafulvenes Containing a Chiral Pendant Hydroxy Group.

Simple enantioselective synthesis of 6,6-disubstituted pentafulvenes bearing chiral pendant hydroxy groups are attained by cascade reactivity using commercially available proline-based organocatalysts. Condensation of cyclopentadiene with the acetyl function of a 1,2-formylacetophenone, followed by cyclization of a resulting fulvene-stabilized carbanion with the formyl group, generates bicyclic chiral alcohols with initial er values up to 94:6. Exceptional enantio-enrichment of the resultant alcohols results upon crystallization-even near racemic samples spontaneously de-racemize. This enables new families of substituted cyclopentadienes that are both enantiomerically and diastereomerically pure to be rapidly attained.

Synthesis of Unimolecular Micelles with Incorporated Hyperbranched Boltorn H30 Polyester modified with Hyperbranched Helical Poly(phenyl isocyanide) Chains and their Enantioselective Crystallization Performance.

Here, the fabrication of unimolecular micelles functionalized with helical polymeric chains as a chiral nucleating agent in enantioselective crystallization is reported. Starting from a fractionated hyperbranched polyester (Boltorn H30), the ring-opening polymerization of l-lactic acid (LLA) and subsequent terminal-group modification affords the alkyne-Pd(II)-anchored hyperbranched macroinitiator (H30-PLLA-Pd). By taking advantage of a Pd(II)-catalyzed living polymerization of chiral pendant modified l- or d-phenyl isocyanide (PI) monomers, well-defined chiral unimolecular micelles (H30-PLLA-PPI) grafted with radiating helical PPI coronas of one predominant screw sense are obtained. The resultant chiral materials demonstrate excellent application in the enantioselective crystallization of racemic threonine in water, and a 92% enantiomeric excess value of the residual solution is obtained. It is believed this present proof of concept and methodology are facile and powerful for preparing novel and versatile chiral materials with different topological structures, not only applicable to PPI but also to other types of polymers.

Helical screw sense bias in chiral polyfluorene stimulated by solvent.

Conjugated homopolymer poly(9,9-bis(3-((S)-2-methylbutylpropanoate))fluorene) (PSF) with chiral pendants was synthesized and characterized. Dissolution experiments show that PSF is well dissolved in racemic limonene at high temperature and begins aggregating upon sequential cooling treatment. The corresponding assemblies were transferred to quartz plate by the spin-coating method. Comparably, film casting from chloroform solution was also prepared. Upon annealing thermal treatments, these PSF films exhibited perfect mirror circular dichroism (CD) Cotton effects and dissymmetry ratios. Optical absorption spectroscopy (UV-vis), CD, and fluorescence spectroscopy results reveal that chiral side chains successfully induced M- and P-helical structures in aggregates and films, and this significant difference was ascribed to their differential supramolecular conformations.

Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC.

A series of optically active poly(diphenylacetylene) derivatives bearing a chiral substituent (poly-2S) or chiral and achiral substituents (poly-(2Sx-co-31−x)) on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenyl)acetylene) with (S)-1-phenylethylamine ((S)-2) or benzylamine (3) in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) were investigated. Poly-2S and poly-(2Sx-co-31−x) (0.06 < x < 0.71) formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2S and h-poly-(2Sx-co-31−x)). Furthermore, h-poly-2S and h-poly-(2S0.36-co-30.64) emitted circularly polarized luminescence with opposite signs. h-Poly-2S showed higher chiral recognition abilities toward a larger number of racemates than poly-2S without a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene) derivative bearing the same chiral substituent on half of its pendant phenyl rings. h-Poly-(2S0.36-co-30.64) also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared with h-poly-2S.