Photon Upconverted Circularly Polarized Luminescence via Triplet–Triplet Annihilation

Circularly polarized luminescent materials are of increasing attention due to their potential applications in advanced optical technologies, such as chiroptical devices and optical sensing. Recently, in all reported circularly polarized luminescent materials, high‐energy excitation results in low‐energy or downconverted circularly polarized luminescence (CPL) emission. Although photon upconversion—i.e., the conversion of low‐energy light into higher‐energy emission, with a wide variety of applications—has been widely reported, the integration of photon upconversion and CPL in one chiral system to achieve higher‐energy CPL emission has never been reported. Herein, a brief review is provided of recent achievements in photon‐upconverted CPL via the triplet–triplet annihilation mechanism, focusing on the amplified dissymmetry factor g_lum through energy transfer process and dual upconverted and downconverted CPL emission through chirality and energy transfer process.     

Generation of doubly charged vortex beam by concentrated loading of glass disks along their diameter

We show that a system of glass disks compressed along their diameters enables one to induce a doubly charged vortex beam in the emergent light when the incident light is circularly polarized. Using such a disk system, one can control the efficiency of conversion of the spin angular momentum to the orbital angular momentum by a loading force. The consideration presented here can be extended for the case of crystalline materials with high optical damage thresholds in order to induce high-power vortex beams.     

Enantiomeric MOF Crystals Using Helical Channels as Palettes with Bright White Circularly Polarized Luminescence

The host–guest chemistry of metal–organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology-like H-bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (g_lum) of the host l /d -CMOF (±1.50 × 10⁻³) to a maximum of ±0.0115 for the composite l /d -CMOF⊃fluorophores. l /d -CMOF⊃fluorophores in pairs generate bright color-tunable CPL and almost ideal white CPL (0.33, 0.32) with a record-high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light-emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.     

Spin-to-orbit conversion at acousto-optic diffraction of light: conservation of optical angular momentum

Acousto-optic diffraction of light in optically active cubic crystals is analyzed from the viewpoint of conservation of optical angular momentum. It is shown that the availability of angular momentum in the diffracted optical beam can be necessarily inferred from the requirements of angular momentum conservation law. As follows from our analysis, a circularly polarized diffracted wave should bear an orbital angular momentum. The efficiency of the spin-to-orbit momentum conversion is governed by the efficiency of acousto-optic diffraction.     

Controlling Chirality across Length Scales using DNA

Nano‐objects with chiral properties attract growing interest due to their relevance for a wide variety of technological applications. For example, chiral nano‐objects may be used in characterization platforms that involve chiral molecular recognition of proteins or in the fabrication of nanomechanical devices such as screw‐gears or nanoswimmers. Spatial ordering of emitters of circularly polarized light might greatly benefit from the utilization of chiral shapes. Tools developed in DNA nanotechnology now allow precise tailoring of the chiral properties of molecules and materials at various length scales. Among others, they have already been applied to control the handedness of helical shapes (configurational chirality) or the chiral positioning of different‐sized nanoparticles at the vertices of tetrahedra (compositional chirality). This work covers some of the key advances and recent developments in the field of chiral DNA nanoarchitectures and discusses their future perspectives and potential applications.     

Full‐Color Tunable Circularly Polarized Luminescent Nanoassemblies of Achiral AIEgens in Confined Chiral Nanotubes

Circularly polarized luminescent (CPL) materials are currently attracting great interest. While a chiral building is usually necessary in order to obtain CPL materials, here, this study proposes a general approach for fabricating 1D circularly polarized luminescent nanoassemblies from achiral aromatic molecules or aggregation‐induced emissive compounds (AIEgens). It is found that a C₃ symmetric chiral gelator can individually form hexagonal nanotube structures and encapsulate the guest molecules. When achiral AIEgens are encapsulated into the confined nanotubes via organogelation, the AIEgens will emit circularly polarized luminescence. Further, the direction of the CPL could be controlled by the supramolecular chirality of the nanotube. Remarkably, the approach is universal and various kinds of the AIEgens can be doped to show such property, providing a full‐color‐tunable circularly polarized luminescence.     

Emergent Nonreciprocal Circularly Polarized Emission from an Organic Thin Film

Controlling circularly polarized (CP) emission is key for both fundamental understanding and applications in the field of chiral photonics and electronics. Here, a completely new way to achieve this goal is presented. A luminescent thin film, made from a chiral conjugated phenylene bis-thiophenylpropynone able to self-assemble into ordered structures, emits highly circularly polarized light with opposite handedness from its two opposite faces. Such emergent nonreciprocal behavior in CP emission, so far unprecedented, represents a fundamental advance, opening new opportunities in design, preparation, and applications of CP emitting materials.     

Experimental Verification of Maxwellian Electrodynamics

The theory of the classical experiment of Beth on measuring the angular momentum of a light beam is considered together with the conclusions reached on the basis of this experiment. It is proposed to illuminate a disk in cosmic space with electromagnetic radiation in order to verify the presence of orbital and spin momenta in a circularly polarized electromagnetic beam.     

Fullerene Desymmetrization as a Means to Achieve Single‐Enantiomer Electron Acceptors with Maximized Chiroptical Responsiveness

Solubilized fullerene derivatives have revolutionized the development of organic photovoltaic devices, acting as excellent electron acceptors. The addition of solubilizing addends to the fullerene cage results in a large number of isomers, which are generally employed as isomeric mixtures. Moreover, a significant number of these isomers are chiral, which further adds to the isomeric complexity. The opportunities presented by single‐isomer, and particularly single‐enantiomer, fullerenes in organic electronic materials and devices are poorly understood however. Here, ten pairs of enantiomers are separated from the 19 structural isomers of bis[60]phenyl‐C61‐butyric acid methyl ester, using them to elucidate important chiroptical relationships and demonstrating their application to a circularly polarized light (CPL)‐detecting device. Larger chiroptical responses are found, occurring through the inherent chirality of the fullerene. When used in a single‐enantiomer organic field‐effect transistor, the potential to discriminate CPL with a fast light response time and with a very high photocurrent dissymmetry factor (g_ph = 1.27 ± 0.06) is demonstrated. This study thus provides key strategies to design fullerenes with large chiroptical responses for use as chiral components of organic electronic devices. It is anticipated that this data will position chiral fullerenes as an exciting material class for the growing field of chiral electronic technologies.     

Photo-Acoustic Spectroscopy Reveals Extrinsic Optical Chirality in GaAs-Based Nanowires Partially Covered with Gold

We report on the extrinsic chirality behavior of GaAs-based NWs asymmetrically hybridized with Au. The samples are fabricated by a recently developed, lithography-free self-organized GaAs growth, with the addition of AlGaAs shell and GaAs supershell. The angled Au flux is then used to cover three-out-of-six sidewalls with a thin layer of Au. Oblique incidence and proper sample orientation can lead to circular dichroism. We characterize this chiral behavior at \( 532\,{\text{nm}} \) and \( 980\,{\text{nm}} \) by means of photo-acoustic spectroscopy, which directly measures the difference in absorption for the circularly polarized light of the opposite headedness. For the first time to our knowledge, circular dichroism is observed in both the amplitude and the phase of the photo-acoustic signal. We strongly believe that such samples can be used for chiral applications, spanning from circularly polarized light emission, to the enantioselectivity applications.     

Circularly polarized laser emission induced by supramolecular chirality in cholesteric liquid crystals

This paper describes the circularly polarized spectroscopic studies on absorption and emission of an achiral fluorescent dye embedded in cholesteric liquid crystals (CLCs). Optical excitation of the dye-doped CLC cell with a linearly polarized laser brought about the two laser emission peaks at longer and shorter reflection band edges of the CLC host through the internal laser feedback effect of the one-dimensional CLC photonic band-gap. At this stage, the optically excited laser emissions showed circularly polarized characteristic, even though the excitation beam was linearly polarized. The circularly polarized direction of the laser emission was determined by molecular chirality of only few mol% of the enantiomeric chiral dopant in this molecular system.     

Plasmonic Chirality and Circular Dichroism in Bioassembled and Nonbiological Systems: Theoretical Background and Recent Progress

Nature is chiral, thus chirality is a key concept required to understand a multitude of systems in physics, chemistry, and biology. The field of optics offers valuable tools to probe the chirality of nanosystems, including the measurement of circular dichroism, the differential interaction strength between matter and circularly polarized light with opposite helicity. Simultaneously, the use of plasmonic systems with giant light-interaction cross-sections opens new paths to investigate and manipulate systems on the nanoscale. Consequently, the interest in chiral plasmonic and hybrid systems has continually grown in recent years, due to their potential applications in biosensing, polarization-encoded optical communication, polarization-selective chemical reactions, and materials with polarization-dependent light–matter interaction. Experimentally, chiral properties of nanostructures can be either created artificially using modern fabrication techniques involving inorganic materials, or borrowed from nature using bioassembly or biomolecular templating. Herein, the recent progress in the field of plasmonic chirality is summarized, with a focus on both the theoretical background and the experimental advances in the study of chirality in various systems, including molecular-plasmonic assemblies, chiral plasmonic nanostructures, chiral assemblies of interacting plasmonic nanoparticles, and chiral metal metasurfaces and metamaterials. The growth prospects of this field are also discussed.     

Modular Molecular Self‐Assembly for Diversified Chiroptical Systems

Bottom‐up multicomponent molecular self‐assembly is an efficient approach to fabricate and manipulate chiral nanostructures and their chiroptical activities such as the Cotton effect and circular polarized luminescence (CPL). However, the integrated coassembly suffers from spontaneous and inherent systematic pathway complexity with low yield and poor fidelity. Consequently, a rational design of chiral self‐assembled systems with more than two components remains a significant challenge. Herein, a modularized, ternary molecular self‐assembly strategy that generates chiroptically active materials at diverse hierarchical levels is reported. N‐terminated aromatic amino acids appended with binding sites for charge transfer and multiple hydrogen bonds undergo the evolution of supramolecular chirality with unique handedness and luminescent color, generating abundant CPL emission with high luminescence dissymmetry factor values in precisely controlled modalities. Ternary coassembly facilitates high‐water‐content hydrogel formation constituted by super‐helical nanostructures, demonstrating a helix to toroid topological transition. This discovery would shed light on developing complicated multicomponent systems in mimicking biological coassembly events.     

One-Dimensional Chiral Copper Iodide Chain-Like Structure Cu4I4(R/S-3-quinuclidinol)3 with Near-Unity Photoluminescence Quantum Yield and Efficient Circularly Polarized Luminescence

Chiral organic−inorganic hybrid metal halide materials have shown great potential for circularly polarized luminescence (CPL) related applications for their tunable structures and efficient emissions. Here, this work combines the highly emissive Cu₄I₄ cubane cluster with chiral organic ligand R/S-3-quinuclidinol, to construct a new type of 1D Cu-I chains, namely Cu₄I₄(R/S-3-quinuclidinol)₃, crystallizing in noncentrosymmetric monoclinic P2₁ space group. These enantiomorphic hybrids exhibit long-term stability and show bright yellow emission with a photoluminescence quantum yield (PLQY) close to 100%. Due to the successful chirality transfer from the chiral ligands to the inorganic backbone, the enantiomers show intriguing chiroptical properties, such as circular dichroism (CD) and CPL. The CPL dissymmetry factor (g_lum) is measured to be ≈4 × 10⁻³. Time-resolved photoluminescence (PL) measurements show long averaged decay lifetime up to 10 µs. The structural details within the Cu₄I₄ reveal the chiral nature of these basic building units, which are significantly different than in the achiral case. This discovery provides new structural insights for the design of high performance CPL materials and their applications in light emitting devices.     

Angular Momentum Balance on Light Reflection

Abstract

It was pointed out by Holbourn in 1936 that there is an apparent breakdown of angular momentum conservation on reflection of circularly polarized light at the plane interface between two lossless dielectrics. The analysis presented in this paper shows that this discrepancy does not arise provided that: (a) the intensities of the incident, reflected, and transmitted beams vanish at large distances from their axes, and (b) the angular momentum of each beam is calculated from first principles.     

Tailoring Chiroptical Activity of Iron Disulfide Quantum Dot Hydrogels with Circularly Polarized Light

Chiral inorganic nanomaterials have recently attracted significant attention because of their many important applications, such as in asymmetric catalysis and chiral sensing. Here, chiral iron disulfide quantum dots (FeS₂ QDs) are synthesized via chirality transfer using l/d ‐cysteine (Cys) as chiral ligands. The chiral FeS₂ QDs are coassembled with two gelators to produce a cogel (l ‐ or d ‐[Gel+FeS₂]) with a g‐factor value of ±0.06. Interestingly, the cogels display intense circularly polarized luminescence. More significantly, the degree of twisting (twist pitch) and the diameter of the cogels can be markedly regulated by illumination with circularly polarized light (CPL) in the ranges of 120–213 and 37–65 nm, respectively, which is caused by the CPL‐induced electron transfer. This research opens the way for the design of chiroptical devices with a wide range of functions and applications.     

Preparation of chiral poly(diacetylene) films from 10,12-pentacosadiynoic acid using circularly polarized light

By irradiating evaporated 10,12-pentacosadiynoic acid (p-DA) monomer film with circularly polarized light (CPL), we prepared chiral poly(diacetylene) [PDA] film. The circular dichroism (CD) was obtained reproducibly, depending on the rotational direction of the CPL. The induced chirality showed the dependence on the substrate temperature used for the preparation of evaporated p-DA monomer films, and it was stable after the transition to red-phase by annealing. Results suggest that side chain of polymer made a significant contribution to the formation of red-phase chiral PDA.     

Angular momentum of the fields of a few-mode fiber. III. Optical Magnus effect, Berry phase, and topological birefringence

It is shown that, on the one hand, the evolution of the angular rotation of the lines of nodes of the CP₁₁ mode is a manifestation of the optical Magnus effect in a few-mode fiber with a parabolic refractive index profile, and, on the other hand, the additional phase γ _b =±δβ ₂₁ z in CV and IV vortices is the Berry topological phase, which arises as a result of the cyclic change in the orientations of the orthogonal axes of dislocations. The splitting of the propagation velocities of orthogonal circularly polarized CV⁺ and IV⁻ modes in an LV vortex in a parabolic fiber is a manifestation of the phenomenon of topological birefringence of a few-mode fiber. The azimuth of the linear polarization of a vortex undergoes continuous angular rotation. In an optical fiber with a stepped index profile the CP₁₁ mode forms circularly polarized edge dislocation over lengths which are multiples of half the beat length, and over lengths which are odd multiples of the quarter beat length it forms linearly polarized fields with a purely screw dislocation. This transformation of edge and screw dislocations can be regarded formally as conversion of the polarizational angular momentum into orbital angular momentum. The conversion of angular momentum is a reflection of the dynamical unity of the optical Magnus effect and the Berry topological phase in the fields of a few-mode fiber. Pis’ma Zh. Tekh. Fiz. 23, 59–67 (December 12, 1997)     

Theoretical Prediction of Chiral 3D Hybrid Organic–Inorganic Perovskites

Hybrid organic–inorganic perovskites (HOIPs), in particular 3D HOIPs, have demonstrated remarkable properties, including ultralong charge‐carrier diffusion lengths, high dielectric constants, low trap densities, tunable absorption and emission wavelengths, strong spin–orbit coupling, and large Rashba splitting. These superior properties have generated intensive research interest in HOIPs for high‐performance optoelectronics and spintronics. Here, 3D hybrid organic–inorganic perovskites that implant chirality through introducing the chiral methylammonium cation are demonstrated. Based on structural optimization, phonon spectra, formation energy, and ab initio molecular dynamics simulations, it is found that the chirality of the chiral cations can be successfully transferred to the framework of 3D HOIPs, and the resulting 3D chiral HOIPs are both kinetically and thermodynamically stable. Combining chirality with the impressive optical, electrical, and spintronic properties of 3D perovskites, 3D chiral perovskites is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.     

Formation of chiral branched nanowires by the Eshelby Twist

Manipulating the morphology of inorganic nanostructures, such as their chirality and branching structure, has been actively pursued as a means of controlling their electrical, optical and mechanical properties. Notable examples of chiral inorganic nanostructures include carbon nanotubes, gold multishell nanowires, mesoporous nanowires and helical nanowires. Branched nanostructures have also been studied and been shown to have interesting properties for energy harvesting and nanoelectronics. Combining both chiral and branching motifs into nanostructures might provide new materials properties. Here we show a chiral branched PbSe nanowire structure, which is formed by a vapour-liquid-solid branching from a central nanowire with an axial screw dislocation. The chirality is caused by the elastic strain of the axial screw dislocation, which produces a corresponding Eshelby Twist in the nanowires. In addition to opening up new opportunities for tailoring the properties of nanomaterials, these chiral branched nanowires also provide a direct visualization of the Eshelby Twist.