Chiroptical Response Research Articles

The N-Oscillator Born–Kuhn Model: An In-Depth Analysis of Chiro-Optical Properties in Complex Chiral Systems

A comprehensive theory is developed for the chiral optical response of two configurations of the N-oscillator Born–Kuhn model (NOBK): the helically stacked and the corner stacked models. In the helical NOBK model, there is always a chiral response regardless of the value of N, whereas in the corner NOBK, only configurations with even N demonstrate a chiral response. Generally, the magnitudes of optical rotatory dispersion (ORD) and circular dichroism (CD) increase with N when the parameters of each oscillator are fixed. In cases of weak coupling, the spectral shapes of ORD and CD remain invariant, while strong coupling significantly alters the spectral shapes. For large damping, the spectral amplitude becomes smaller, and the spectral features become broader. In the presence of small damping, strong coupling introduces degeneracy in the coupled oscillator system, leading to multiple spectral features in both ORD and CD across the entire spectral region. This simple model can not only help in the design of tunable chiral metamaterials but also enhance our understanding of chiro-optical responses in structures with different configurations.

Controlling Chiroptical Responses via Chemo-Mechanical Deformation of DNA Origami Structures.

DNA origami-based templates have been widely used to fabricate chiral plasmonic metamaterials due to their precise control of the placement of nanoparticles (NPs) in a desired configuration. However, achieving various chiroptical responses inevitably requires a change in the structure of DNA origami-based templates or binding sites on them, leading to the use of significantly different sets of DNA strands. Here, we propose an approach to controlling various chiroptical responses with a single DNA origami design using its chemo-mechanical deformation induced by DNA intercalators. The chiroptical response could be finely tuned by altering the concentration of intercalators only. The silver (Ag) enhancement was used to amplify the chiroptical signal by enlarging NPs and to maintain it by stiffening the template DNA structure. Furthermore, the sensitivity in the chiroptical signal change to the concentration of intercalators could be modulated by the type of intercalator, the mixture of two intercalators, and the stiffness of DNA origami structures. This approach would be useful in a variety of optical applications that require programmed spatial modification of chiroptical responses.

Giant Apparent Optical Circular Dichroism in Thin Films of Bismuth‐Based Hybrid Organic–Inorganic Metal Halide Semiconductor Through Preferred Orientation

AbstractIntroducing chirality into organic/inorganic hybrid materials can impart chiroptical properties such as circular dichroism. The ability to tune chiroptical properties in self‐assembled materials can have important implications for spintronic and optoelectronic applications. Here, a chiral organic cation, (R/S)‐4‐methoxy‐α‐methylbenzylammonium, is incorporated to synthesize the bismuth‐based hybrid organic–inorganic metal halide semiconductor, (R/S‐MeOMePMA)BiI4. Thin films of this Bi‐based compound demonstrate large chiroptical responses, with circular dichroism anisotropy (gCD) values up to ≈0.1, close to the highest value observed in another chiral metal‐halide semiconductor, (R‐MBA2CuCl4). Detailed investigation reveals that this large gCD in (R/S‐MeOMePMA)BiI4 is caused by the apparent CD effect. Careful selection of deposition conditions and the concomitant thin‐film orientation enables the control of gCD, with maximum value observed when its thin film has a well‐crystallized preferred (001) orientation parallel to the substrate. The results support a growing body of evidence that low symmetry plays an important role in achieving unusually large gCD in these chiral metal–halide materials and provides design rules for achieving large chiroptical response via morphology control.

Highly Circularly Polarized Light‐Sensitive Chiral One‐Dimensional Perovskites Enabled by Antisolvent Engineering

AbstractChiral perovskites have emerged as promising next‐generation materials for polarization detection due to their excellent circularly polarized light (CPL) detection capabilities. However, they suffer from a low chiroptical response when fabricated as a polycrystalline thin film, limiting their potential range of applications. Herein, it is demonstrated that antisolvent dripping during the spin‐coating process can effectively improve the chiroptical properties of polycrystalline chiral perovskite thin films. Systematic analysis with different antisolvents reveals that the highly polar antisolvent chloroform interacts with dimethyl sulfoxide molecules via hydrogen bonding. This strong hydrogen bonding suppresses the formation of intermediate and secondary phases and accelerates the crystallization of chiral 1D perovskites, thus reducing the density of the iodine vacancies inside the perovskite thin films. The lower density of iodine vacancies also intensifies the asymmetric tilting inorganic distortion of PbI6 octahedrons, enhancing the chiroptical response of the fabricated chiral perovskite material. Photodetectors based on the chloroform‐treated chiral perovskite films achieve a remarkably high distinguishability of 0.31, outperforming previously reported photodetectors based on the chiral perovskites. The fabricated photodetectors also exhibit outstanding responsivity and detectivity with enhanced operational stability.

Helicene‐type β‐isoindigo‐based boron‐dipyrromethene analogs with strong near‐infrared chiroptical activity

AbstractNear‐infrared (NIR) chiroptical response has been less explored because it is challenging to achieve both chirality and NIR absorption/emission. Herein, we describe the design of heterohelicene‐type β‐isoindigo‐based boron‐dipyrromethene (BODIPY) analogs (β‐IBs), which shift the absorption peak to 800 nm and produce significant Cotton effects (127.8 M−1 cm−1) and absorbance dissymmetry factors (|gabs| = 3.5 × 10−3). The luminescence dissymmetry factor (glum) and circularly polarized luminescence (CPL) brightness (BCPL) of up to 1.24 × 10−3 and 1.78 M−1 cm−1 were realized beyond 800 nm. These β‐IBs are the first examples of helicene‐type compounds with the highest gabs in the NIR region and CPL beyond 800 nm. Theoretical calculations demonstrate that the strong chiroptical activities are triggered by their large transition magnetic dipole moments. This study not only provides a new approach to the synthesis of a larger variety of unprecedented helicene‐type BODIPY analogs but also demonstrates excellent NIR chiroptical properties.

Magnetic assembly of plasmonic chiral superstructures with dynamic chiroptical responses.

Plasmonic nanostructures exhibiting dynamically tunable chiroptical responses hold great promise for broad applications such as sensing, catalysis, and enantioselective analysis. Despite the successful fabrication of chiral structures through diverse templates, creating dynamic chiroptical materials with fast and reversible responses to external stimuli is still challenging. This work showcases reversible magnetic assembly and active tuning of plasmonic chiral superstructures by introducing a chiral magnetic field from a cubic permanent magnet. Manipulating the strength and direction of the magnetic field controls both the chiral arrangement and plasmonic coupling of the nanoparticle assembly, enabling fast and reversible tunability in not only the handedness of the superstructures but also the spectral characteristics of their chiroptical properties. The dynamic tunability further enables the fabrication of color-changing optical devices based on the optical rotatory dispersion effect, showcasing their potential for application in anti-counterfeiting and stress sensors.

Nanoparticle manipulation based on chiral plasmon effects.

Chiral plasmonic structures have garnered increasing attention owing to their distinctive chiroptical response. Localized surface plasmon resonance can significantly enhance the circular dichroism and local electromagnetic field of chiral plasmonic structures, resulting in enhanced electromagnetic forces acting on surrounding nanoparticles. Moreover, the circular dichroism response of chiral structures provides an effective means for macroscopic adjustment of microscopic electromagnetic fields. However, chiral plasmon effects are naturally related to angular momentum, and particle control studies of chirality usually focus on angular momentum. This paper proposes a particle manipulation method utilizing chiral light-matter interactions. Through optimization of the optical response of the chiral structure, the direction of electromagnetic forces exerted on surrounding polystyrene particles reverses upon a change in the incident light's handedness. According to this characteristic, the movement direction control of polystyrene particles with a diameter of 100 nm was achieved. By altering the handedness of a single circularly polarized light, more than 94% high-precision particle manipulation was achieved, reducing the complexity of particle manipulation. This microfluidic method has significant implications for advancing microfluidic research and chiral applications.

Bilayer Metasurface with High-Q Terahertz Chiroptical Response Empowered by Intrinsic Quasi-Multi-Bound States in the Continuum

Bilayer Metasurface with High-Q Terahertz Chiroptical Response Empowered by Intrinsic Quasi-Multi-Bound States in the Continuum

Tunable multiband circular dichroism and asymmetric transmission enabled by chiral quasi-BICs in dielectric metasurfaces covered with graphene

High-Q chiral resonances have attracted great interest recently due to their practical photonic applications. For generating such resonances, chiral quasi-bound states in the continuum (quasi-BICs) have recently been proposed and experimentally demonstrated by many researchers, while their dynamic tunability has still not been discussed. In this work, we show multiband circular dichroism and asymmetric transmission based on high-Q chiral quasi-BICs in dielectric metasurfaces, which are dynamically tunable in the mid-infrared range by using graphene monolayers covering the metasurfaces. By changing the Fermi energy, the surface conductivity of graphene is tunable in a wide range, resulting in tunable chiroptical responses of the metasurfaces. Since the metasurfaces exhibit high-Q resonances with narrow linewidths, tuning the metasurfaces results in large modulation depths of circular dichroism and asymmetric transmission, which is of great importance for photonic applications, including tunable polarization manipulation and polarization-dependent detection.

Chiroptical properties of cyanine aggregates: hierarchical modelling from monomers to bundles.

Some achiral cyanine dyes form well-ordered chiral assemblies exhibiting pronounced Circular Dichroism (CD) and Circularly Polarized Luminescence (CPL). Notably, achiral C8O3 cyanines self-assemble into tubular J-aggregates, which further organize into bundles displaying bisignate CD spectrum - hallmark of an exciton coupled system - and an unusual bisignated CPL. In contrast, the tubular aggregates display a monosignate CD spectrum. The mechanism underlying these intriguing features remains elusive. In the present work, a quantum-mechanical exciton model is proposed to elucidate the (chir)optical behaviour of C8O3 aggregates. A herringbone arrangement of C8O3 dyes within the tubular aggregates well reproduces the observed spectral signatures. The anomalous observation of a singular CD peak in tubular aggregates is ascribed to the intrinsic chirality of the monomeric units inside the aggregate, whereas the CD doublet characterizing the bundles is attributed to the exciton coupling between the constituent tubes. The bisignated CPL signal observed in bundles reveals significant anti-Kasha emission at room temperature and is quantitatively addressed accounting for a very tiny exciton splitting leading to a sizable thermal population of both exciton states. This study provides crucial insights on the complexity of C8O3 aggregation and on the origin of chiroptical response at various aggregation stages.

Observation of Magnetic Quadrupole Endowed Helical Dichroism in Artificial Propeller Meta‐Molecules

AbstractThis study demonstrates that the magnetic quadrupole (MQ) can make an indispensable contribution to helical dichroism (HD), which is distinct from HD caused by electric quadrupole (EQ). Specifically, the established multipole expansion theory of the light–matter interaction reveals that EQ‐induced HD belongs to the pure electric dipole–quadrupole (E1‐E2) excitation, while newly discovered MQ‐induced HD belongs to the pure magnetic dipole‐quadrupole (M1‐M2) excitation. Metallic propeller meta‐molecules are used to elaborate on this novel physical mechanism and demonstrate that HD can be significantly enhanced and flexibly tuned by increasing stereo twist of propeller meta‐molecules or slightly focusing the linearly polarized vortex beam to improve the orbital angular momentum number. Importantly, the aforementioned intriguing phenomena are validated by fabricating stereo twisted propeller meta‐molecules via nano‐kirigami method. The findings reveal a paradigm‐shift approach to manipulate the chiroptical response of a single metallic nanostructure via photonic orbital angular moment, opening prospects for optical encryption, communication, next‐generation chiroptical spectroscopy, and chiral vortex optical devices.

Unrestricted Chiral Patterning by Laser Writing in Liquid Crystalline and Plasmonic Nanocomposite Thin Films.

Obtaining hierarchical structures with arbitrarily controlled chirality remains a challenge. Here, thin films featuring chiroptically bipolar patterns are produced by a device utilizing microscale photothermal re-melting of materials exhibiting chirality synchronization. This device operates autonomously, guided by an algorithm that facilitates the homochiral growth of supramolecular organic helices through controlling their re-melting. The chirality synchronization phenomena of constitutionally achiral molecules grants availability of both handednesses of the helices, enabling unrestricted chiral writing in the film. The collective chiroptical response of assembled molecules is utilised to guide the patterning process, creating a foundation for optically secured information. The established methodology enables achieving dissymmetry factor values for circular dichroism (CD) a magnitude higher than previously reported, as confirmed with state-of-the-art, synchrotron-based Mueller matrix polarimetry (MMP). Moreover, the developed method is extended to nanocomposites comprising gold nanoparticles, providing the opportunity to tune the CD toward the plasmonic region. This strategic application of photothermal processing, specifically laser-directed melting, uncovers the potential to broaden the selection of nanostructured materials with precisely designed functionalities for photonic applications.

Homochiral Nanopropeller via Chiral Active Surface Growth.

Under the control of chiral ligand glutathione and in the presence of hexadecyltrimethylammonium bromide, Au deposition on Au seeds is known to give chiral nanostructures. We have previously shown that the protruding chiral patterns, as opposed to flat facets, are likely caused by active surface growth, where nonuniform ligand coverage could be responsible for the focused growth at a few active sites. By pushing the limit of such a growth mode, here, we use decahedral seeds to prepare homochiral nanopropellers with intricate patterns of deep valleys and protruding ridges. Control experiments show that the focused growth depends on the rates of Au deposition by changing either the seed concentration or the reductant concentration, consistent with the proposed mechanism. The dynamic growth competition between the ligand-deficient active sites and the ligand-rich surfaces gradually focuses the growth onto a few active sites, causing the expansion of grooves, squeezing of steep ridges, and a surprising 36° rotation of the pentagonal outline. The imbalanced deposition on the prochiral slopes is responsible for the tilted grooves, the twisted walls, and thus the well-separated and distorted blades, which become the origin of the chiroptical responses.

Inversion of the Chiroptical Responses of Chiral Gold Nanoparticles with a Gold Film.

The deposition of chiral nanoparticles (NPs) onto various substrates is crucial for the fabrication of high-density photonic devices. Understanding the interaction of chiral light and chiral NPs supported on substrates is essential for developing optical sensors and modulators. However, the chiroptical responses of plasmonic chiral NPs on substrates have remained elusive. Here we provide an important understanding of the correlation between the substrate material and the chiroptical response. The scattering dissymmetry factors of individual chiral Au nanocubes are inverted and enhanced with a gold film. Qualitative theories are proposed to analyze the observed variations in the chiroptical signals of chiral NPs on different substrates. Our results offer an encouraging route for modulating and amplifying the chiroptical signals in the use of chiral NPs in light control, light-based quantum technologies, and sensing.

Can Magnetic Dipole Transition Moment Be Engineered?

AbstractThe development of chiral compounds with enhanced chiroptical properties is an important challenge to improve device applications. To that end, an optimization of the electric and magnetic dipole transition moments of the molecule is necessary. Nevertheless, the relationship between chemical structure and such quantum mechanical properties is not always clear. That is the case of magnetic dipole transition moment (m) for which no general trends for its optimization have been suggested. In this work we propose a general rationalization for improving the magnitude of m in different families of chiral compounds. Performing a clustering analysis of hundreds of transitions, we have been able to identify a single group in which |m| value is maximized along the helix axis. More interestingly, we have found an accurate linear relationship (up to R2=0.994) between the maximum value of this parameter and the area of the inner cavity of the helix, thus resembling classical behavior of solenoids. This research provides a tool for the rationalized synthesis of compounds with improved chiroptical responses.

Can Magnetic Dipole Transition Moment Be Engineered?

The development of chiral compounds with enhanced chiroptical properties is an important challenge to improve device applications. To that end, an optimization of the electric and magnetic dipole transition moments of the molecule is necessary. Nevertheless, the relationship between chemical structure and such quantum mechanical properties is not always clear. That is the case of magnetic dipole transition moment (m) for which no general trends for its optimization have been suggested. In this work we propose a general rationalization for improving the magnitude of m in different families of chiral compounds. Performing a clustering analysis of hundreds of transitions, we have been able to identify a single group in which |m| value is maximized along the helix axis. More interestingly, we have found an accurate linear relationship (up to R2 =0.994) between the maximum value of this parameter and the area of the inner cavity of the helix, thus resembling classical behavior of solenoids. This research provides a tool for the rationalized synthesis of compounds with improved chiroptical responses.

DNA-Modulated and Mechanoresponsive Excitonic Couplings Reveal Chiroptical Correlation of Conformation, Tension, and Dynamics of DNA Self-Assembly.

Study of the conformational and mechanical behaviors of biomolecular assemblies is vital to the rational design and realization of artificial molecular architectures with biologically relevant functionality. Here, we revealed DNA-modulated and mechanoresponsive excitonic couplings between organic chromophores and verified strong correlations between the excitonic chiroptical responses and the conformational and mechanical states of DNA self-assemblies irrespective of fluorescence background interference. Besides, the excitonic chiroptical effect allowed sensitive monitoring of DNA self-assembled nanostructures due to small molecule bindings or DNA strand displacement reactions. Moreover, we developed a new chiroptical reporter, a DNA-templated dimer of an achiral cyanine5 and an intrinsically chiral BODIPY, that exhibited unique multiple-split spectral line shape of exciton-coupled circular dichroism, largely separated response wavelengths, and enhanced anisotropy dissymmetry factor (g-factor). These results shed light on a promising chiroptical spectroscopic tool for studying biomolecular recognition and binding, conformation dynamics, and soft mechanics in general.

Decoding Polarization in a Single Achiral Gold Nanostructure from Emitted Far-Field Radiation.

The emergence of optical chirality in the light emitted from plasmonic nanostructures is commonly associated with their geometrical chirality. Although it has been demonstrated that even achiral structures can exhibit chiral near-fields, the existence of chiroptical far-field responses of such structures is widely neglected. In this paper, we present a detailed analysis of the polarization state in a single planar achiral plasmonic nanostructure that sustains more than one prominent plasmon mode. In consideration of the relative phase, the superposition of the fields associated with these modes determines the polarization state of the emitted light in the far-field. Supported by simulations of the surface charge distribution of the particle, we show that the polarization state of the emitted light is already determined in the near-field. The chiroptical far-field responses are analyzed by polarized single-particle dark-field scattering spectroscopy. We introduce an analytical model that enables us to obtain the polarization information from the spectra of structures with dipolar resonances taken under unpolarized illumination. The same principle is confirmed in polarimetric spectroscopy measurements on rhomboids with systematically varied angles, therefore, introducing increasing values of geometrical chirality to the structures. The agreement between the calculation and measurement demonstrates the general validity of our model for both chiral and achiral structures.

Determination of Enantiomeric Excess by Optofluidic Microlaser near Exceptional Point.

Enantiomeric excess (ee) is an essential indicator of chiral drug purification in the pharmaceutical industry. However, to date the ee determination of unknown concentration enantiomers generally involves two separate techniques for chirality and concentration measurement. Here, a whispering-gallery mode (WGM) based optofluidic microlaser near exceptional point to achieve the ee determination under unknown concentration with a single technique is proposed. Exceptional point induces the unidirectional WGM lasing, providing the optofluidic microlaser with the novel capability to measure chirality by polarization, in addition to wavelength-based concentration detection. The dual-parameters detection of optofluidic microlaser empowers it to achieve ee determination of various unknown enantiomers without additional concentration measurements, a feat that is challenging to accomplish with other methods. Featuring the sensitivity enhancement and miniature structure of the WGM sensors, the obtained chiroptical response of the present approach is ≈30-fold higher than that of the conventional optical rotation-based polarimeter, and the reagent consumption is reduced by three orders of magnitude.

Phase-change metasurfaces for dynamic control of chiral quasi-bound states in the continuum

Chiral quasi-bound states in the continuum (QBIC) offer novel mechanisms to achieve intrinsic chiroptical responses. However, current studies on chiral QBIC metasurfaces are restricted to the excitation of intrinsic chirality and fail to dynamically control its circular dichroism (CD) responses. Herein, we construct a phase-change metasurface based on paired Ge2Sb2Te5 (GST) bars to demonstrate the dynamic control of the CD responses of chiral QBIC. The modified coupled mode theory (CMT) is proposed to evaluate the intrinsic chirality, and the predicted results are in good agreement with the finite–difference time-domain (FDTD) results. The maximal intrinsic chirality is associated with the spin-selected dipole mode, i.e., the coupled magnetic dipole (MD) QBIC mode for the left-handed circularly polarized (LCP) light and the decoupled electric dipole (ED) QBIC mode for the right-handed circularly polarized (RCP) light. By varying the volume fraction of GST, the location of chiral BIC can be tuned linearly, and the corresponding chiral response can be switched.