Transient chirality inversion during racemization of a helical cobalt(III) complex.

SignificanceWe first observed a transient chirality inversion on a simple unimolecular platform during the racemization of a chiral helical complex [LCo3A6]3+, i.e., the helicity changed from P-rich (right-handed) to M-rich (left-handed), which then racemized to a P/M equimolar mixture in spite of the absence of a reagent that could induce the M helix. This transient chirality inversion was observed only in the forward reaction, whereas the reverse reaction showed a simple monotonic change with an induction time. Consequently, the M helicity appeared only in the forward reaction. These forward and reverse reactions constitute a hysteretic cycle. Compounds showing such unique time responses would be useful for developing time-programmable switchable materials that can control the physical/chemical properties in a time-dependent manner.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Sign Inversion of Circularly Polarized Luminescence in Cholesteric Liquid Crystals Induced by Mercury Ions through Binaphthyl Dopants' Conjugation Control.

Stimuli-responsive circularly polarized luminescence (CPL) materials based on cholesteric liquid crystal (CLC) platforms show great promise for applications in information encryption and anticounterfeiting. In this study, we constructed a mercury ion-responsive CPL system in CLCs by controlling the conjugation degree of axially chiral binaphthyl derivatives. Two chiral binaphthyl derivatives (R/S-1 and R/S-2) were initially used as chiral dopants to demonstrate that CPL inversion (glum values from 0.5/-0.44 to -0.53/0.48) in CLCs could be achieved by modulating the conjugation degree of the chiral binaphthyls. Based on this concept, the thioacetal binaphthyl R-2S was developed and used as a mercury-responsive chiral dopant in CLCs. Under Hg ion treatment, the CPL sign inverted (glum value changed from 0.22 to -0.29) due to the transformation of the thioacetal into an aldehyde group. Additionally, the mercury ion-responsive CPL material was applied in information encryption.

Ligand-Assisted Self-Assembly of 3D Perovskite Nanocrystals into Chiral Inorganic Quasi-2D Perovskites (n = 3) with Ligand-Ratio-Dependent Chirality Inversion.

Chiral inorganic quasi-2D perovskites are prepared by self-assembling 3D perovskites in solution for the first time. The quasi-2D perovskite synthesized is a pure-phase perovskite with = 3 and is periodically arranged, which is a big breakthrough in quasi-2D inorganic perovskites.  With the individual chiral CsPbBr3 nanocrystals (NCs) assemble into quasi-2D perovskite, the g-factor significantly improved (≈5 × 10-3 ). In addition, the chiroptical activity of quasi-2D perovskites is explored to be improved with the lateral size increasing. In the first stage of assembly, chiral optical activity is increased due to the lateral size-dependent optical activity, while the changes in the later stages are attributable to the chiral morphology. Interestingly, chirality inversion is found to be correlated to the number of ligands. It is believed that different conformers of chiral ligands caused by steric hindrance of the original ligand oleylamine result in opposite circular dichroism (CD) polarities. The chirality inversion phenomenon is universal, regardless of the choice of ligands. This work opens up a new path for the synthesis of quasi-2D perovskites and provides more opportunities for the modulation of chiral optical activity.

Assembly of Helical Nanostructures: Solvent-Induced Morphology Transition and Its Effect on Cell Adhesion.

Being able to precisely manipulate both the morphology and chiroptical signals of supramolecular assemblies will help to better understand the natural biological self-assembly mechanism. Two simple l/d-phenylalanine-based derivatives (L/DPFM) have been designed, and their solvent-dependent morphology evolutions are illustrated. It was found that, as the content of H2 O in aqueous ethanol solutions was increased, LPFM self-assembles first into right-handed nanofibers, then flat fibrous structures, and finally inversed left-handed nanofibers. Assemblies in ethanol and H2 O exhibit opposite conformations and circular dichroism (CD) signals even though they are constructed from the same molecules. Thus, the morphology-dependent cell adhesion and proliferation behaviors are further characterized. Left-handed nanofibers are found to be more favorable for cell adhesion than right-handed nanostructures. Quantitative AFM analysis showed that the L929 cell adhesion force on left-handed LPFM fibers is much higher than that on structures with inversed handedness. Moreover, the value of cell Young's modulus is lower for left-handed nanofibrous films, which indicates better flexibility. The difference in cell-substrate interactions might lead to different effects on cell behavior.

A Photo- and Thermo-Driven Azoarene-Based Circularly Polarized Luminescence Molecular Switch in a Liquid Crystal Host.

The development of chiral optical active materials with switchable circularly polarized luminescence (CPL) signals remains a challenge. Here an azoarene-based circularly polarized luminescence molecular switch, (S, R, S)-switch 1 and (R, R, R)-switch 2, are designed and prepared with an (R)-binaphthyl azo group as a chiral photosensitive moiety and two (S)- or (R)-binaphthyl fluorescent molecules with opposite or the same handedness as chiral fluorescent moieties. Both switches exhibit reversible trans/cis isomerization when irradiated by 365 nm UV light and 520 nm green light in solvent and liquid crystal (LC) media. In contrast with the control (R, R, R)-switch 2, when switch 1 is doped into nematic LCs, polarization inversion and switching-off of the CPL signals are achieved in the resultant helical superstructure upon irradiation with 365 nm UV and 520 nm green light, respectively. Meanwhile, the fluorescence intensity of the system is basically unchanged during this switching process. In particular, these variations of the CPL signals could be recovered after heating, realizing the true sense of CPL reversible switching. Taking advantage of the unique CPL switching, the proof-of-concept for "a dual-optical information encryption system" based on the above CPL active material is demonstrated.

Realizing Abundant Chirality Inversion of Supramolecular Nanohelices by Multiply Manipulating the Binding Sites in Molecular Blocks.

The induction of diverse chirality regulation in nature by multiple binding sites of biomolecules is ubiquitous and plays an essential role in determining the biofunction of biosystems. However, mimicking this biological phenomenon and understanding at a molecular level its mechanism with the multiple binding sites by establishing an artificial system still remains a challenge. Herein, abundant chirality inversion is achieved by precisely and multiply manipulating the co-assembled binding sites of phenylalanine derivatives (D/LPPF) with different naphthalene derivatives (NA, NC, NP, NF). The amide and hydroxy group of naphthalene derivatives prefer to bind with the carboxy group of LPPF, while carboxylic groups and fluoride atoms tend to bind with the amide moiety of LPPF. All these diverse interaction modes can precisely trigger helicity inversion of LPPF nanofibers. In addition, synergistically manipulating the carboxy and amide binding sites from a single LPPF molecule to simultaneously interact with different naphthalene derivatives leads to chirality regulation. Typically, varying the solvent may switch the interaction modes and the switched new interaction modes can be employed to further regulate the chirality of the LPPF nanofibers. This study may provide a novel approach to explore chirality diversity in artificial systems by regulating the intermolecular binding sites.

pH and Salt-Assisted Macroscopic Chirality Inversion of Gadolinium Coordination Polymer.

The precise adjustment of handedness of helical architectures is important to regulate their functions. Macroscopic chirality inversion has been achieved in organic supramolecular systems by pH, metal ions, solvents, chiral and non-chiral additives, temperature, and light, but rarely in coordination polymers (CPs). In particular, salt-assisted macroscopic chirality inversion has not been reported. In this work, we carried out a systematic investigation on the role of pH and salt in regulating the morphology of CPs based on Gd(NO3)3 and R-(1-phenylethylamino)methylphosphonic acid (R-pempH2). Without extra NO3-, the chirality inversion from the left-handed superhelix R-M to the right-handed superhelix R-P can be achieved by pH modulation from 3.2 to 3.8. The addition of NaNO3 (2.0 eq) at pH 3.8 results in an inversion of chiral sense from R-P to R-M as a pure phase. To our knowledge, this is the first example of salt-assisted macroscopic helical inversion in artificial systems.

Kinetic Co-assembly Pathway Induced Chirality Inversion Along with Morphology Transition.

Kinetic co-assembly pathway induced chirality inversion along with morphology transition is of importance to understand biological processes, but still remains a challenge to realize in artificial systems. Herein, helical nanofibers consisting of phenylalanine-based enantiomers (L/DPF) successfully transform into kinetically trapped architectures with opposite helicity through a kinetic co-assembly pathway. By contrast, the co-assemblies obtained by a thermodynamic pathway exhibit non-helical structures. The formation sequence of non-covalent interactions plays a crucial role in structural chirality of co-assemblies. For the kinetic pathway, the hydrogen bonding between D/LPF and naphthylamide derivatives forms before π-π stacking to facilitate the formation of helical structures with inverse handedness. This study may provide an approach to explore chirality inversion accompanied by morphology transition by manipulating the kinetic co-assembly pathway.

Redox-Triggered Chirality Switching and Guest-Capture/Release with a Pillar[6]arene-Based Molecular Universal Joint.

A chiral electrochemically responsive molecular universal joint (EMUJ) was synthesized by fusing a macrocyclic pillar[6]arene (P[6]) to a ferrocene-based side ring. A single crystal of an enantiopure EMUJ was successfully obtained, which allowed, for the first time, the definitive correlation between the absolute configuration and the circular dichroism spectrum of a P[6] derivative to be determined. The self-inclusion and self-exclusion conformational change of the EMUJ led to a chiroptical inversion of the P[6] moiety, which could be manipulated by both solvents and changes in temperature. The EMUJ also displayed a unique redox-triggered reversible in/out conformational switching, corresponding to an occupation/voidance switching of the P[6] cavity, respectively. This phenomenon is an unprecedented electrochemical manipulation of the capture and release of guest molecules by supramolecular hosts.

Ligand Exchange Strategy for Tuning of Helicity Inversion Speeds of Dynamic Helical Tri(saloph) Metallocryptands.

We developed a new strategy, ligand exchange strategy, for tuning the response speeds of helicity inversion of a metal-containing helical structure. This is based on the exchange of the two axial amine ligands of the octahedral Co3+ centers in the metallocryptands [LCo3 X6 ] (X=axial amine ligand). The response speeds of the helicity induction were controlled by using different combinations of achiral and chiral amines as the starting and entering ligands, respectively. The response speeds of the helicity inversion from P to M were also tuned by using different combinations of chiral amines.

Solvent polarity effects on supramolecular chirality of a polyfluorene-thiophene copolymer.

This study demonstrates the supramolecular chirality control of a conjugated polymer via solvent polarity. We designed and synthesized a chiral polyfluorene-thiophene copolymer having two different chiral side chains at the 9-position of the fluorene unit. Chiral cyclic and alkyl ethers with different polarities were selected as the chiral side chains. The sign of the circular dichroism spectra in the visible wavelength region was affected by the solvent system, resulting from the change of supramolecular structure. The estimation of the solubility parameter revealed that the solubility difference of the side chains contributed to the change of the circular dichroism sign, which was also observed in spin-coated films prepared from good solvents having different polarities.

Water-Binding-Mediated Gelation/Crystallization and Thermosensitive Superchirality.

Determination of molecular structural parameters of hydrophobic cholesterol-naphthalimide conjugates for water binding capabilities as well as their moisture-sensitive supramolecular self-assembly were revealed. Water binding was a key factor in leading trace water-induced crystallization against gelation in apolar solvent. Ordered water molecules entrapped in self-assembly arrays revealed by crystal structures behave as hydrogen-bonding linkers to facilitate three-dimensional growth into crystals rather than one-dimensional gel nanofibers. Water binding was also reflected on the supramolecular chirality inversion of vesicle self-assembly in aqueous media via heating-induced dehydration. Structural parameters that favor water binding were evaluated in detail, which could help rationally design organic building units for advancing soft materials, crystal engineering, and chiral recognition.

The Cooperative Effect of Both Molecular and Supramolecular Chirality on Cell Adhesion.

Although helical nanofibrous structures have great influence on cell adhesion, the role played by chiral molecules in these structures on cells behavior has usually been ignored. The chirality of helical nanofibers is inverted by the odd-even effect of methylene units from homochiral l-phenylalanine derivative during assembly. An increase in cell adhesion on left-handed nanofibers and weak influence of cell behaviors on right-handed nanofibers are observed, even though both were derived from l-phenylalanine derivatives. Weak and negative influences on cell behavior was also observed for left- and right-handed nanofibers derived from d-phenylalanine, respectively. The effect on cell adhesion of single chiral molecules and helical nanofibers may be mutually offset.

Temperature-Driven Planar Chirality Switching of a Pillar[5]arene-Based Molecular Universal Joint.

The study of an enantiopure bicyclic pillar[5]arene-based molecular universal joint (MUJ) by single-crystal X-ray diffraction allowed for the first time the unequivocal assignment of the absolute configuration of a planar chiral pillar[5]arene by circular dichroism spectroscopy. Crucially, the absolute configuration of the MUJ was switched reversibly by temperature, with an accompanying sign inversion of the anisotropy factor that varied by as much as 0.03, which is the largest value ever reported. Mechanistically, the reversible chirality switching of the MUJ is driven by the threading/dethreading motion of the fused ring and hence is dependent on both the size and nature of the ring and the solvent employed, reflecting the critical balance between the self-complexation of the ring by pillar[5]arene, the solvation to the excluded ring, and the inclusion of solvent molecules in the cavity.

Dynamic Inversion of Stereoselective Phosphate Binding to a Bisurea Receptor Controlled by Light and Heat.

A chiral bisurea anion receptor, derived from a first-generation molecular motor, can undergo photochemical and thermal isomerization operating as a reconfigurable system. The two possible cis configurations in the isomerization cycle are opposite in helicity, as is shown by CD spectroscopy. (1)H NMR titrations demonstrate that the P and M helical cis isomers hold opposite enantioselectivity in the binding of binol phosphate, while anion complexation by the intermediate trans isomer is not selective. The difference in the binding affinity of the enantiomers was rationalized by DFT calculations, revealing very distinct binding modes. Thus, the enantiopreferred substrate binding in this receptor can be inverted in a dynamic fashion using light and heat.

A Highly Efficient Chirality Switchable Synthesis of Dihydropyran-Fused Benzofurans by Fine-Tuning the Phenolic Proton of ß-Isocupreidine (ß-ICD) Catalyst with Methyl.

A highly enantioselective ß-isocupreidine (ß-ICD) catalyzed synthesis of dihydropyran-fused benzofurans through [4+2] cycloaddition of allenoates and benzofuranone alkenes was developed. Switchable chirality inversion of cycloaddition products was achieved by replacing the phenolic proton of the catalyst with a methyl, demonstrating an amazing effect of minimal structural variation on inverting enantioselectivity. DFT calculations were utilized to elucidate the origin of the observed phenomena. Computation also provided a clue for a rational design in which the multi-hydrogen bond with the alcohol additive was found to improve the enantioselectivity of the cycloaddition. Finally, the substrate scope was examined, in which a number of functionalized dihydropyran-fused benzofurans could be obtained in high yields (up to 97 %) with very good regio- (>20:1) and enantioselectivities (up to 98:2 e.r.).

Photoisomerization and thermal reconstruction induced supramolecular chirality inversion in nanofiber determined by minority isomer.

Here, amphiphile GCH based on glutamide-cyanostilbene is designed and synthesized, it is found that it can assembly in acetonitrile, and shows circular dichroism signals. After Z-E isomerizaition by UV irradiation, the CD signal of the assembly can be inverted. Unexpectedly, after another heating and cooling process, the circular dichroism signals can be totally inverted even though the E-isomers are in minority. Finally, the molecular dynamics (MD) simulations deeply elucidate the supramolecuar chirality inversion mechanism. This work brings some new insights into the control of chirality inversion, which may provide a perspective for the smart chiroptical materials construction.

Circularly Polarized Luminescence Chirality Inversion and Dual Anticounterfeiting Labels Based on Fluorescent Cholesteric Liquid Crystal Particles.

The development of materials with circularly polarized luminescence (CPL) properties is a promising but challenging frontier in advanced materials science. Modulating the chiral properties of chiral polymers has also been a focus of research. Studies have been conducted to control the ground-state chirality of chiral polymers by adjusting the concentration of the chiral dopant. However, the chirality inversion of CPL of fluorescent liquid crystal particles by chiral dopant concentration has not been reported. Here, we report the preparation of fluorescent cholesteric liquid crystal (FCLC) particles that display polarizable structural color and CPL, demonstrating how varying the chiral dopant amount can reverse the CPL direction, leading to systems where the rotation directions of polarizable structural color and CPL either align or differ. This study confirmed the critical role played by the formation of the twist grain boundary phase in inducing the inversion of the ground-state chirality of FCLC particles and, subsequently, triggering the inversion process of CPL chirality. Furthermore, it leverages chiral structural color and fluorescence of FCLC particles to develop a sophisticated dual verification system. This system, utilizing both circularly polarized light and fluorescence, offers enhanced anticounterfeiting protection for high-value items.

Full-Color Circularly Polarized Luminescence of Supramolecular Polymers with Handedness Inversion Regulated by Anion and Temperature.

Constructing full-color circularly polarized luminescence (CPL) materials with switchable handedness in the solid state is an appealing yet considerably challenging task, especially for supramolecular polymer films assembled from homochiral monomers. Herein, supramolecular polymers with full-color CPL and inverted handedness are realized through the coassembly of a homochiral cholesterol derivative (PVPCC), metal ions (Zn2+), and achiral fluorescent dyes. The obtained coassembled systems show anion-directed supramolecular chirality inversion by exchanging the anions of NO3-, ClO4-, BF4-, and Cl-. For instance, the negative CD and right-handed CPL are detected in the PVPCC/Zn(NO3)2 aggregates, which convert into positive CD and left-handed CPL after introducing Cl-, corresponding to the transformation from nanorods to nanofibers. Furthermore, the tunable CPL color and handedness inversion of the coassembly system of PVPCC/Zn(NO3)2 and achiral fluorescent dyes can be established by alternately changing the assembling temperature of 298 and 273 K. Importantly, the full-color CPL polymeric materials are then constructed by doping the PVPCC/Zn(NO3)2/dyes complexes into poly(methyl methacrylate) (PMMA) film, which maintains the handedness inversion and shows the enhanced CPL performance. The work not only deepens the understanding of chirality inversion in supramolecular chemistry but also helps to construct full-color CPL materials with switchable handedness from homochiral building blocks in materials science.