Spatiotemporal-Dependent Confinement Effect of Bubble Swarms Enables a Fractal Hierarchical Assembly with Promoted Chirality.

The submarine-confined bubble swarm is considered an important constraining environment for the early evolution of living matter due to the abundant gas/water interfaces it provides. Similarly, the spatiotemporal characteristics of the confinement effect in this particular scenario may also impact the origin, transfer, and amplification of chirality in organisms. Here, we explore the confinement effect on the chiral hierarchical assembly of the amphiphiles in the confined bubble array stabilized by the micropillar templates. Compared with the other confinement conditions, the assembly in the bubble scenario yields a fractal morphology and exhibits a unique level of the chiral degree, ordering, and orientation consistency, which can be attributed to the characteristic interfacial effects of the rapidly formed gas/water interfaces. Thus, molecules with a balanced amphiphilicity can be more favorable for the promotion. Not limited to the pure enantiomers, chiral amplification of the enantiomer-mixed assembly is observed only in the bubble scenario. Beyond the interfacial mechanism, the fast formation kinetics of the confined liquid bridges in the bubble scenario endows the assembly with the tunable hierarchical morphology when regulating the amphiphilicity, aggregates, and confined spaces. Furthermore, the chiral-induced spin selectivity (CISS) effect of the fractal hierarchical assembly was systematically investigated, and a strategy based on photoisomerization was developed to efficiently modulate the CISS effect. This work provides insights into the robustness of confined bubble swarms in promoting a chiral hierarchical assembly and the potential applications of the resulting chiral hierarchical patterns in solid-state spintronic and optical devices.

Aggregate-state-dependent photochromism and circularly polarized luminescence of a chiral biquinoline amphiphile.

The photophysical and chiroptical properties of a chiral biquinoline amphiphile were found to be closely related to its aggregate states. Photochromism through photo-induced radical and circularly polarized luminescence were realized in its gel state and thin film state, respectively.

Handedness-Inverted and Stimuli-Responsive Circularly Polarized Luminescent Nano/Micromaterials Through Pathway-Dependent Chiral Supramolecular Polymorphism.

The precise manipulation of supramolecular polymorphs has been widely applied to control the morphologies and functions of self-assemblies, but is rarely utilized for the fabrication of circularly polarized luminescence (CPL) materials with tailored properties. Here, this work reports that an amphiphilic naphthalene-histidine compound (NIHis) readily self-assembled into distinct chiral nanostructures through pathway-dependent supramolecular polymorphism, which shows opposite and multistimuli responsive CPL signals. Specifically, NIHis display assembly-induced CPL from the polymorphic keto tautomer, which become predominant during enol-keto tautomerization shifting controlled by a bulk solvent effect. Interestingly, chiral polymorphs of nanofiber and microbelt with inverted CPL signals can be prepared from the same NIHis monomer in exactly the same solvent compositions and concentrations by only changing the temperature. The tunable CPL performance of the solid microbelts is realized under multi external physical or chemical stimuli including grinding, acid fuming, and heating. In particular, an emission color and CPL on-off switch based on the microbelt polymorph by reversible heating-cooling protocol is developed. This work brings a new approach for developing smart CPL materials via supramolecular polymorphism engineering.

Stepwise Solution-Interfacial Nanoarchitectonics for Assembled Film with Full-Color and White-Light Circularly Polarized Luminescence.

The fabrication of chiral thin films with tunable circularly polarized luminescence (CPL) colors is important in developing chiroptical materials but remains challenging due to the lack of assembly-initiated chiral film formation methodology. Here, by adopting a combined solution aggregation and interfacial assembly strategy, we report the fabrication of chiral film materials with full-color and white-light CPL. A biquinoline glutamic acid ester (abbreviated as BQGE) shows a typical aggregation-induced emission property with blue CPL after solution aggregation. Subsequent interfacial assembly of these solution aggregates on a solid substrate leads to the formation of a CPL active film consisting of nanobelt structures. Since the BQGE molecule has a coordination site, the CPL emission of an individual BQGE film can be extended from blue to green emission upon coordination with a zinc ion, accompanied by morphology transition from nanobelts to nanofibers. Further extension to red-color CPL is successfully achieved by coassembly with an achiral acceptor dye. Interestingly, the proper combination of coordination ratio and acceptor loading ratio provides bright white-light CPL emission from the BQGE/Zn2+/PDA triad composite film. This work provides a new approach to fabricating chiroptical film materials with controlled microscopic morphology and tunable CPL properties.

Self-Assembled Charge-Transfer Chiral π-Materials: Stimuli-Responsive Circularly Polarized Luminescence and Chiroptical Photothermic Effects.

Despite significant achievements in the field of chiroptical organic materials, the full utilization of both the excited state and ground state chiroptical properties in a single supramolecular system is still rarely disclosed. Here, we report that the rational combination of the charge-transfer (CT) interaction with the spacer effect and controlled protonation of π-histidine leads to chiroptical organic π-materials with both circularly polarized luminescence (CPL) and the supramolecular chirality-directed chiroptical photothermic effect. Three pyrene-conjugated histidine derivatives with varied acyl linkers (PyHis, PyC1His, and PyC3His) were designed to coassemble with electron-deficient 1,2,4,5-tetracyanobenzene (TCNB), leading to the formation of supramolecular CT complexes with intense orange to red CPL depending on the linker length. The linker length also affected the protonation-induced CPL responsiveness of the corresponding CT assemblies. Upon protonation of the histidine moiety, PyC3His/TCNB CT assemblies exhibited an inverted CPL signal, while PyHis/TCNB pairs gave quenched CPL due to the disassembly. The protonation-controlled PyC3His/TCNB CT assemblies at varied pH values showed different chiroptical photothermic effects (CPEs) for the same incident chiral light despite the molecular chirality of PyC3His remaining unchanged, supporting an interesting supramolecular chirality-directed photothermic effect.

Hierarchically self-assembled homochiral helical microtoroids.

Fabricating microscale helical structures from small molecules remains challenging due to the disfavoured torsion energy of twisted architectures and elusory chirality control at different hierarchical levels of assemblies. Here we report a combined solution-interface-directed assembly strategy for the formation of hierarchically self-assembled helical microtoroids with micrometre-scale lengths. A drop-evaporation assembly protocol on a solid substrate from pre-assembled intermediate colloids of enantiomeric binaphthalene bisurea compounds leads to microtoroids with preferred helicity, which depends on the molecular chirality of the starting enantiomers. Collective variable-temperature spectroscopic analyses, electron microscopy characterizations and theoretical simulations reveal a mechanism that simultaneously induces aggregation and cyclization to impart a favourable handedness to the final microtoroidal structures. We then use monodispersed luminescent helical toroids as chiral light-harvesting antenna and show excellent Förster resonance energy transfer ability to a co-hosted chiral acceptor dye, leading to unique circularly polarized luminescence. Our results shed light on the potential of the combined solution-interface-directed self-assembly approach in directing hierarchical chirality control and may advance the prospect of chiral superstructures at a higher length scale.

Pseudo-resonance structures in chiral alcohols and amines and their possible aggregation states.

We now report that some chiral compounds, like alcohols, which are not sterically hindered atropisomers nor epimer mixtures, exhibit two sets of simultaneous NMR spectra in CDCl3. Some other chiral alcohols also simultaneously exhibit two different NMR spectra in the solid state because two different conformers, A and B had different sizes because their corresponding bond lengths and angles are different. These structures were confirmed in the same solid state by X-ray. We designate these as pseudo-resonance for a compound exhibiting several different corresponding lengths that simultaneously coexist in the solid state or liquid state. Variable-temperature NMR, 2D NMR methods, X-ray, neutron diffraction, IR, photo-luminesce (PL) and other methods were explored to study whether new aggregation states caused these heretofore unknown pseudo-resonance structures. Finally, eleven chiral alcohols or diols were found to co-exist in pseudo-resonance structures by X-ray crystallography in a search of the CDS database.

Intramolecular Energy and Solvent-Dependent Chirality Transfer within a BINOL-Perylene Hetero-Cyclophane.

Multichromophoric macrocycles and cyclophanes are important supramolecular architectures for the elucidation of interchromophoric interactions originating from precise spatial organization. Herein, by combining an axially chiral binaphthol bisimide (BBI) and a bay-substituted conformationally labile twisted perylene bisimide (PBI) within a cyclophane of well-defined geometry, we report a chiral PBI hetero-cyclophane (BBI-PBI) that shows intramolecular energy and solvent-regulated chirality transfer from the BBI to the PBI subunit. Excellent spectral overlap and spatial arrangement of BBI and PBI lead to efficient excitation energy transfer and subsequent PBI emission with high quantum yield (80-98 %) in various solvents. In contrast, chirality transfer is strongly dependent on the respective solvent as revealed by circular dichroism (CD) spectroscopy. The combination of energy and chirality transfer affords a bright red circularly polarized luminescence (CPL) from the PBI chromophore by excitation of BBI.

Double helical π-aggregate nanoarchitectonics for amplified circularly polarized luminescence.

The canonical double helical π-stacked array of base pairs within DNA interior has inspired the interest in supramolecular double helical architectures with advanced electronic, magnetic and optical functions. Here, we report a selective-recognized and chirality-matched co-assembly strategy for the fabrication of fluorescent π-amino acids into double helical π-aggregates, which show exceptional strong circularly polarized luminescence (CPL). The single crystal structure of the optimal combination of co-assemblies shows that the double-stranded helical organization of these π-amino acids is cooperatively assisted by both CH-π and hydrogen-bond arrays with chirality match. The well-defined spatial arrangement of the π-chromophores could effectively suppress the non-radiative decay pathways and facilitate chiral exciton couplings, leading to superior CPL with a strong figure of merit (glum = 0.14 and QY = 0.76). Our findings might open a new door for developing DNA-inspired chiroptical materials with prominent properties by enantioselective co-assembly initiated double helical π-aggregation.

Chiral macrocycle-induced circularly polarized luminescence of a twisted intramolecular charge transfer dye.

The host-guest binding between a chiral macrocycle and an achiral dye could suppress the twisted intramolecular charge transfer (TICT) process, leading to enhanced emission and bright circularly polarized luminescence (CPL) from the originally achiral TICT-dye.

Solvent-regulated chiral exciton coupling and CPL sign inversion of an amphiphilic glutamide-cyanostilbene.

The chiral exciton couplings within a Y-shaped amphiphilic glutamide-cyanostilbene (GCS) could be significantly biased by solvent polarity and hydration effects, which led to sign inversion of both the circular dichroism and circularly polarized luminescence of the GCS assemblies.

Self-assembled Möbius strips with controlled helicity.

Different from molecular level topology, the development of supramolecular topology has been limited due to a lack of reliable synthetic methods. Here we describe a supramolecular strategy of accessing Möbius strip, a fascinating topological object featured with only a single edge and single side. Through bending and cyclization of twisted nanofibers self-assembled from chiral glutamate amphiphiles, supramolecular nano-toroids with various twist numbers were obtained. Electron microscopic techniques could clearly identify the formation of Möbius strips when twist numbers on the toroidal fibers are odd ones. Spectroscopic and morphological analysis indicates that the helicity of the Möbius strips and nano-toroids stems from the molecular chirality of glutamate molecules. Therefore, M- and P-helical Möbius strips could be formed from L- and D-amphiphiles, respectively. Our experimental results and theoretical simulations may advance the prospect of creating chiral topologically complex structures via supramolecular approach.

Circularly polarized luminescence of nanoassemblies via multi-dimensional chiral architecture control.

Circularly polarized luminescence (CPL) materials are currently an important class of chiroptical materials that are attracting increasing interest. Nanoassemblies constructed from chiral or achiral building blocks show great potential for achieving CPL-active nanomaterials with high quantum yields and dissymmetry factors, which is crucial for further applications. In nanoassemblies, the dimensional morphology affects the chiroptical properties significantly since the microscopic packing modes will affect the luminescence processes and chirality transfer processes. In this review, we will show some examples for illustrating the relationship between multi-dimensional morphology and chiroptical properties. Furthermore, with dimensional morphology tuning, higher dissymmetry factors would be obtained. We hope to provide a useful and powerful insight into the design and control of CPL-active nanoassemblies via morphology control.

Diaza-Crown Ether-Bridged Chiral Diphosphoramidite Ligands: Synthesis and Applications in Asymmetric Catalysis.

A small library of diaza-crown ether-bridged chiral diphosphoramidite ligands was prepared. In the rhodium-catalyzed asymmetric hydrogenation and hydroformylation reactions, these ligands exhibited distinct properties in catalytic activity and/or enantioselectivity. Hydrogenated products with opposite absolute configurations could be obtained in high yields with excellent ee values by utilizing (S,S)-L1 and (S,S)-L3, respectively. Meanwhile, the addition of alkali metal cations caused variations in catalytic outcomes, showing the supramolecular tunability of these Rh/diphosphoramidite catalytic systems.

Histidine Proton Shuttle-Initiated Switchable Inversion of Circularly Polarized Luminescence.

Switchable inversion of the sign of circularly polarized luminescence (CPL) in chiral supramolecular systems has gained remarkable interest because of its role in understanding the chirality-switching phenomena in biological systems and developing smart chiral luminescent materials. Herein, inspired by the histidine proton shuttle in natural enzymes, we synthesized a histidine π-gel (PyC3H) and realized reversible inversion of supramolecular chirality and CPL by receiving and then transferring a proton. It was found that in the course of histidine protonation by adding an external proton source, the transcription of intrinsic molecular chirality of PyC3H to the supramolecular level biased, achieving dynamic control over the PyC3H gel with left-handed CPL inversed into the right-handed one. The mechanism study revealed that the supramolecular chirality and CPL inversion are mainly affected by the cooperation adjustment of hydrogen bonds and π-π stacking upon histidine protonation and deprotonation, which causes the re-orientations of pyrene chromophores. This work sets up an alternative effective method to fabricate tunable CPL-active materials while using the same chiral small molecules, which provides a new insight into developing bio-inspired switchable supramolecular materials.

Dimension-Tunable Circularly Polarized Luminescent Nanoassemblies with Emerging Selective Chirality and Energy Transfer.

The selective interplay between dimensional morphology transition and signal transfer is an important feature for both nanomaterials and biosystems. While most of those reported examples considered either dimensional transition or signal transfer, the integrated interplay or selectivity for these two aspects in single self-assembled system has been rarely studied. Here, we report that a positively charged chiral π-building block could self-assemble into multidimensional nanostructures, which showed tunable circularly polarized luminescence (CPL). Impressively, when these CPL-active multidimensional structures interacted with two achiral dyes (positively charged ThT and negatively charged CNA), 3D nanocubes and 0D nanospheres showed neither chirality transfer nor energy transfer, while 2D nanoplates could successfully trigger a selective chirality or energy transfer depending on the charge type of acceptor dyes, which then emitted an enhanced CPL signal. This work demonstrated rational design of charged π-building block for the construction of dimension controllable and selective signal transfer self-assembly system, which might deepen the understanding the interplay of dimensional structures and signal transfer functions in natural and nano systems.

Host-guest interaction enabled chiroptical photo-switching and enhanced circularly polarized luminescence.

A cyanostilbene conjugated gelator was incorporated into the cavities of cyclodextrins via the host-guest interaction and the resulting supra-gelator from γ-CyD enabled chiroptical photo-switching, while the other gels showed enhanced circularly polarized luminescences.

Self-Assembly through Coordination and π-Stacking: Controlled Switching of Circularly Polarized Luminescence.

Multiple noncovalent interactions can drive self-assembly through different pathways. Here, by coordination-assisted changes in π-stacking modes between chromophores in pyrene-conjugated histidine (PyHis), a self-assembly system with reversible and inversed switching of supramolecular chirality, as well as circularly polarized luminescence (CPL) is described. It was found that l-PyHis self-assembled into nanofibers showing P-chirality and right-handed CPL. Upon ZnII coordination, the nanofibers changed into nanospheres with M-chirality, as well as left-handed CPL. The process is reversible and the M-chirality can change to P-chirality by removing the ZnII ions. Experimental and theoretical models unequivocally revealed that the cooperation of metal coordination and π-stacking modes are responsible the reversible switching of supramolecular chirality. This work not only provides insight into how multiple noncovalent interactions regulate self-assembly pathways.

Cooperative Chirality and Sequential Energy Transfer in a Supramolecular Light-Harvesting Nanotube.

By constructing a supramolecular light-harvesting chiral nanotube in the aqueous phase, we demonstrate a cooperative energy and chirality transfer. It was found that a cyanostilbene-appended glutamate compound (CG) self-assembled into helical nanotubes exhibiting both supramolecular chirality and circularly polarized luminescence (CPL). When two achiral acceptors, ThT and AO, with different energy bands were co-assembled with the nanotube, the CG nanotube could transfer its chirality to both of the acceptors. The excitation energy could be transferred to ThT but only be sequentially transferred to AO. During this process, the CPL ascribed to the acceptor could be sequentially amplified. This work provides a new insight into the understanding the cooperative chirality and energy transfer in a chiral supramolecular system, which is similar to the natural light-harvesting antennas.

Achiral non-fluorescent molecule assisted enhancement of circularly polarized luminescence in naphthalene substituted histidine organogels.

A naphthalene substituted histidine derivative was found to form an organogel showing circularly polarized luminescence (CPL) and the addition of non-fluorescent achiral benzoic acids could efficiently enhance the CPL via non-covalent interactions.