Circularly polarized luminescence (CPL) from quantum dots (QDs) is interesting for quantum optics, spintronics, and chiral photonics. We report CPL from Si QDs covalently functionalized via vinyl or acetylene linkers with structurally chiral binaphthyl-based ligands, investigating the interplay between binding geometry, surface structure, and chiroptical response. Circular dichroism (CD) spectroscopy reveals that monodentate ligands do not induce chiral transitions associated with the QD, indicating ineffective chirality transfer. In contrast, bidentate vinyl-bridged ligands induce clear, mirror-image CD and circularly polarized luminescence (CPL) signals associated with electronic transitions from the QD, confirming successful chirality transfer. ATR-IR spectroscopy shows that these chiral binaphthyl ligands transition from bidentate to monodentate binding with increasing surface coverage, correlating with a nonmonotonic trend in electronic absorption and bandedge emission dissymmetry factors, gabs and glum with maxima at 2.34 × 10-3 and 8.87 × 10-4 respectively which peak at ∼3 ligands per QD. High-resolution transmission electron microscopy reveals that ligand binding induces lattice compression in the QDs, likely associated with chirality. These findings highlight the crucial role of ligand binding geometry and surface-induced structural distortion in generating chiroptical activity in Si QDs for next-generation chiral nanomaterials.

Although carbohelicenes are attractive circularly polarized luminescence (CPL) emitters, they often suffer from low fluorescence quantum yields and relatively modest luminescence dissymmetry factor (glum), resulting in limited CPL brightness. Here, we report the modulation of the photophysical and chiroptical properties of [7]helicene through the formation of imidazole-based push-pull systems. A series of diaryl imidazole derivatives bearing electron-donating and electron-withdrawing substituents was synthesized, and selected compounds were obtained in enantiomerically pure form. Imidazole incorporation markedly enhances fluorescence quantum yields and molar absorption coefficients, while preserving blue emission (λem ≈ 452-457 nm). Although absorption and luminescence dissymmetry factors decrease compared to the parent helicene, the combined increase in molar attenuation coefficient at the excitation wavelength (ε) and fluorescence quantum yields (Φ) leads to a substantial enhancement of CPL brightness. The best-performing derivatives exhibit up to a 15-fold increase in CPL brightness (BCPL) relative to unsubstituted [7]helicene. These results identify imidazole-based push-pull functionalization as an effective strategy for improving the overall CPL performance of helicenes.

Developing chiral luminescent materials integrating high-contrast stimuli-responsiveness with circularly polarized luminescence (CPL) remains a major challenge. Herein, we report a new pair of enantiomeric dinuclear Cu(I) complexes ((4S,7R)-1 and (4R,7S)-1) constructed from tailored chiral pyridyl-pyrazole ligands. These complexes exhibit not only distinct CPL but also high-contrast, reversible stimuli-responsive luminescence in the solid state. SCXRD, PXRD, FT-IR, and DFT calculations collectively reveal that the emission switching triggered by grinding and CH2Cl2 fuming originates from a reversible crystalline-to-amorphous phase transition, driven by the cleavage and reformation of weak intermolecular interactions, particularly the key pyrazole-N-H···O (perchlorate) hydrogen bonds. Crucially, the emission color contrast is effectively modulated by the enantiopure 1,1,2-trimethylcyclopentane chiral auxiliary moieties (4S,7R and 4R,7S) appended to the ligands, thus underscoring the decisive role of chiral configuration in tuning luminescent properties. This work establishes a versatile chiral ligand engineering strategy and offers valuable insights into the rational design of advanced chiral stimuli-responsive luminescent materials.

ConspectusOver the past three decades, discrete metal-organic cages (MOCs) have captured significant interest as a versatile class of supramolecular architectures. MOCs are discrete molecular assemblies of organic ligands and metal nodes (ions/clusters) that possess an intrinsic porosity. Unlike extended frameworks (MOFs), their discrete nature affords superior solution processability, modifiability, and structural tunability. Collectively, these attributes underpin diverse applications in molecular recognition, catalysis, separation, optics, and so on.Building on their discrete nature, MOCs' predesigned architectures inherently facilitate postsynthetic modification (PSM), enabling the installation of new functional groups and properties via the tailored modification of linkers, metal nodes, pores, or surface environments. To date, a number of stable MOCs have been reported, several of which have been utilized for PSM, such as paddle-wheel Cu-MOCs and hydrothermally stable Zr-MOCs. The development of these stable precursors has unlocked new avenues for functionalization, transcending the limitations of direct synthesis.In 2017, we reported the first example of anionic coordination titanium tetrahedra (Ti4L6) featuring calixarene-like coordination-active vertices. Self-assembled from mononuclear Ti nodes and rigid-flexible hydroxycarboxylate ligands, these cages possess unique structural features. Specifically, they exhibit excellent solution processability and abundant active sites (e.g., exposed oxygen atoms and naphthalene rings), which render them ideal for hierarchical assembly (including PSM). Since then, substantial progress in this area has enabled the generation of a diverse range of structures.In this Account, we systematically summarize these developments, focusing on four key pathways: (1) surface modification for catalysis and circularly polarized luminescence (CPL); (2) coordination-assembled cage-based frameworks for molecular recognition/separation; (3) supramolecular assembly (H-bonding/π-π stacking) for nonlinear optics (NLO); and (4) template-directed synthesis of rare cage-supported MOFs for enhanced NLO. Notably, this Account addresses the existing gap in integrating the "precursor design → hierarchical assembly → functional application" pipeline for Ti4L6 cages, providing a coherent conceptual framework for researchers in supramolecular chemistry and materials science. Finally, the future perspectives for Ti4L6 cages are discussed to guide further innovation in this evolving field.

Circularly polarized luminescence (CPL) is a key enabling technology for next-generation photonics, yet developing materials combining high stability, brightness, and dissymmetry factor (glum) remains a formidable challenge. A promising strategy involves solidifying highly-ordered emissive liquid crystals into robust polymer networks, but this process is often hindered by polymerization-induced stress that destroys the delicate chiral architecture. Here, we establish design principles to overcome this paradox through a synergistic co-design of monomer and network. We discover that fluorene-based monomers combining core planarity and segmental flexibility facilitate near-ideal helical assembly, achieving an exceptional fluidic glum of 0.60. Critically, employing a topologically-matched bifunctional crosslinker minimizes network stress, successfully preserving this elite performance to yield a robust thermoset with a record-high final glum of 0.54. In this work, we show that this rational strategy effectively bridges the gap between ideal fluidic systems and practical solid-state materials, paving the way for advanced chiroptical applications.

Er3+-doped 1540nm light-emitting diodes (LEDs) are critical components in optical communications C-band, non-trunk communication, bioimaging, and sensing. However, integrating high luminous efficiency with tailored circularly polarized luminescence (CPL) in such LEDs remains a critical challenge. Here, we demonstrate efficient 1540nm short-wave infrared (SWIR) electroluminescence with distinct CPL in Cs3ErCl6 nanocrystals (NCs)-based LEDs via a synergistic strategy of Sb3+/Y3+ co-doping and camphor ligand modification. Y3+ doping modulates lattice symmetry, inducing Stark splitting of the Er3+ energy level and enhancing luminescence intensity. Sb3+ introduction triggers efficient self-trapped excitons emission at 530nm, whose energy levels match Er3+ states to boost energy transfer efficiency. Subsequently, camphor ligand exchange passivates Er3+-related defects, increasing the 1540nm photoluminescence quantum yield to 35.7% and endowing NCs with CPL (asymmetry factor: -3.67 × 10-2) via camphor's chiral structure. SWIR LEDs based on camphor-modified Cs3Er0.7Y0.3Cl6: Sb3+ NCs exhibit a record-high external quantum efficiency of 3.06% at 1540nm, and first, demonstrate electrically-driven circularly polarized 1540nm emission with asymmetry factor of -3.08 × 10-2. This work presents a synergistic doping-ligand strategy for Er-based halide optoelectronics, offering a versatile platform to develop high-performance long-wavelength devices with integrated efficient emission and tailored polarization, crucial for advancing next-generation optical communication and bioimaging.

Catalytic asymmetric synthesis of boron-stereogenic compounds has garnered growing interest in recent years. However, strategies for constructing boron-stereogenic centers with structural diversity remain underdeveloped, especially compared with the well-established methods for carbon stereocenters formation. Herein, we report an earth-abundant cobalt-catalyzed enantioselective C-H activation/desymmetric annulation of arylamides with prochiral boron-diyne compounds, providing direct access to a wide range of boron-stereogenic heterocycles. Enabled by a cobalt(II)/chiral salicyloxazoline (Salox) catalytic system, this approach effectively addresses the challenge of precise differentiation between two enantiotopic alkyne units. The transformation concurrently establishes a stable boron-stereogenic center together with multiple chiral axes (N-N or C-N) in a single step, featuring a broad substrate scope, good functional group tolerance, and high efficiency. Gram-scale synthesis, directing-group removal, and versatile derivatizations further highlighted the synthetic utility of this strategy. Detailed experimental and computational studies provide in-depth insight into the catalytic mechanism. Notably, the obtained optically pure compounds exhibit promising photoluminescence and circularly polarized luminescence (CPL) properties, underscoring their potential for advanced optical applications.

Chiral hybrid metal halides (CHMHs) have emerged as a promising class of ionic crystalline materials for circularly polarized luminescence (CPL). In these materials, organic cations primarily act as chirality sources, whereas the inorganic frameworks serve as the luminescent centers. The interactions between chiral organic cations and inorganic frameworks enable intrinsic CPL emission. The soft and ionic nature of CHMHs further distinguishes them from conventional covalent luminophores, offering exceptional structural and chiroptical tunability. This tutorial review summarizes recent progress in CPL-active CHMHs, focusing on the fundamental routes for CPL generation, amplification and application. Representative synthetic strategies for CHMHs are introduced, followed by an analysis of luminescence mechanisms and their relevance to CPL generation. Key strategies to enhance CPL performance, including composition engineering and external-field regulation, are also reviewed. Beyond fundamental understanding, emerging applications enabled by the unique properties of CHMHs, including circularly polarized light-emitting diodes, CPL-resolved scintillators, and anti-counterfeiting technologies, are summarized. Finally, key challenges and future perspectives are outlined to guide the development of high-performance CHMH-based chiroptical materials and devices.

Circularly polarized luminescent (CPL) materials are gaining prominence in next-generation optoelectronic technologies, including 3D displays, optical data storage, smart sensors and chiroptical light sources for asymmetric synthesis. The inherent limitations associated with tedious synthetic protocols has limited the use of a wide variety of organic systems as CPL emitters. In this work, we report a novel and facile strategy to achieve chiral light emission from achiral porphyrin supramolecular assemblies, thereby overcoming the inherent challenges associated with the use of this class of molecules in CPL investigations. A series of porphyrin derivatives appended with four dipicolylamine units, in the presence of l/d-mandelic acid and zinc(ii) ions, formed supramolecular aggregates exhibiting chiroptical responses. The porphyrin undergoes self-assembly following an isodesmic model of polymerization, resulting in uniform chiral microflowers exhibiting high CPL activity. Systematic investigations on the specific interactions at the molecular level helped probe the mechanism of ground and excited-state optical activity. Notably, when incorporated in polymeric films, the self-assembled structures retained their CPL activity, showcasing the potential application of the microflowers as chiral light emitting materials. The fundamental molecular understanding of chiral induction in achiral porphyrin derivatives paves the way for the development of CPL-active materials across a broader range of organic fluorophores.

Near-infrared (NIR) circularly polarized luminescent (CPL) materials are highly desirable for optical communication, bioimaging, night-vision applications, and chiral encrypted information transfer, yet their practical use is limited by extremely low luminescence asymmetry factors (glum). Here, we establish a helical photonic confinement strategy by embedding NIR-emissive Au13 nanoclusters into chiral nematic mesoporous silica (CNMS). Precise matching between the chiral photonic bandgap and cluster emission yields strongly enhanced NIR-CPL with a glum of -0.4, enabling direct discrimination of left- and right-handed circularly polarized emission in the NIR region. This system realizes the first high-contrast, CPL-resolved near-infrared (night-vision) imaging based on intrinsic cluster emission, without external polarization optics. The Au13 clusters undergo reversible assembly-disassembly within helical nanochannels, allowing controllable NIR-CPL switching and handedness inversion. Mechanistic studies confirm that the CPL enhancement originates from chiral photonic propagation modulation rather than intrinsic emitter chirality. This helical-confinement principle is extendable to multicolor metal clusters, offering a general route toward high-efficiency CPL materials.

The melting and vitrification behavior of metal-organic materials endows them with high processability, enabling the formation of bulk solids with potential in optical applications. Nevertheless, obtaining metal-organic glasses with chiroptical properties, such as circularly polarized luminescence (CPL), remains challenging due to the limited thermal and mechanical stability of current chiral metal-organic materials. Here, we report a pair of homochiral copper(I) cyanide complexes based on 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) that can be readily vitrified by either melt-quenching or desolvation. Structural analysis reveals that vitrification disrupts only the intermolecular stacking of the complexes, while preserving the local coordination environment. The resulting melt-quenched glasses are CPL-active and exhibit yellow-orange triplet excited state decay via thermally activated delayed fluorescence (TADF) at room temperature, which is environment-dependent due to an additional 3BINAP↔3(Cu→BINAP) CT (CT = charge transfer) equilibrium. Centimeter-sized monoliths and thin films can be fabricated by molding and thermal annealing, highlighting their excellent processability. Moreover, the glasses can be recrystallized by solvent vapor treatment, which triggers distinct changes in luminescent properties. These results establish BINAP-based copper(I) cyanide complexes as a versatile platform for the design of CPL-active metal-organic glasses and point to their promise in optoelectronic applications.

The development of smart circularly polarized luminescence (CPL) materials faces significant challenges, primarily centered on achieving high luminescence dissymmetry factors (glum) alongside broadly tunable responses. Here, we report a chiral scaffold based on covalent organic frameworks (COFs) for high-performance and adaptive photocontrollable time-evolving CPL, enabling identifiable and encrypted chiroptical outputs. Cyclodextrin modified on the COF generates multicolor CPL emission through noncovalent interaction with fluorophores. Blending the modified COF and fluorophores with polyethylene glycol (PEG) yields transparent mixed-matrix films exhibiting a high glum of -0.027 and absolute quantum yield (39%). Subsequently, sulfonato-merocyanine, a photochromic switch, is introduced to modulate the system's emission, endowing the reversible CPL signals with light-fueled tunability and time-dependent dynamic evolution. Notably, we fabricate mixed-matrix films to amplify the light-controllable CPL signals, where the glum varies between -0.009 and -0.044 upon 420 nm irradiation and thermal relaxation. A dynamic modulation range of glum ≈0.035 is achieved, which is a remarkable value reported among dynamic COF-based CPL materials. Furthermore, films featuring photocontrollable, self-erasable vector luminescent signals are achieved for dual-mode anticounterfeiting. This work provides insight into the design of intelligent luminescent materials.

Constructing chiral metal halides without relying on chiral organic cations offers exceptional compositional and structural freedom, yet their rational design remains challenging due to the limited understanding of the origins of structural chirality. Here, by employing the achiral 4-benzylpiperidine (4-BPP) cation and controlling the crystallization pathways, we access two distinct manganese bromide polymorphs: centrosymmetric α-(4-BPP)2MnBr4 (space group I2/a) and chiral β-(4-BPP)2MnBr4 (space group P21). Detailed crystallographic analysis reveals that asymmetric hydrogen-bonding interactions at the organic-inorganic interface of β-(4-BPP)2MnBr4 amplify the distortion of [MnBr4]2- tetrahedra, driving symmetry breaking and giving rise to inherent chirality. The resulting chiral phase exhibits anti-thermal-quenching green-red dual emission, in which the red component originates from distortion-induced self-trapped excitons and is further modulated via energy transfer from green-emissive Mn2+ centers. Consequently, dual-color tunable circularly polarized luminescence (CPL) is realized in chiral metal halides for the first time, featuring a large dissymmetry factor (glum) of 7×10-2. Moreover, the non-centrosymmetric crystal structure enables efficient second- and third-harmonic generation. These findings elucidate how hydrogen-bonding interactions govern structural chirality at the molecular level and establish a general design principle for engineering chiroptical and nonlinear optical properties in metal halides.

ConspectusChirality imparts spin to light─the intrinsic fingerprint of asymmetric matter. When optical spin interacts with molecular or supramolecular chirality, it generates distinctive chiroptical phenomena, with circularly polarized luminescence (CPL) attracting significant attention due to its optical activity and spin angular momentum. This asymmetric coupling enables the development of functional CPL-active materials, driving advancements in intelligent information interactions, including stereoscopic displays, secure information technologies, advanced imaging, and quantum photonics. For practical use, effective CPL-active materials demand the integration of high chiroptical activity for strong signals, robust stability for reliable performance, and processability for device integration. Conventional chiral nanomaterials and organic emitters typically exhibit dissymmetry factors of only 10-4-10-2, far below the theoretical maximum of ±2. In contrast, structural engineering strategies─such as supramolecular assemblies, chiral photonic crystals (particularly chiral liquid crystals), and plasmonic coupling─can amplify chiroptical activity to dissymmetry factors above 10-1. However, in some cases, these systems are restricted to fluidic or film states, hindering their further integration into applicable devices. The key challenge, therefore, is to create CPL-active materials with strong performance and, subsequently, to endow these materials with sufficient stability and processability to enable device construction for practical applications.To address this challenge, we leverage supramolecular helical templates and coassemble them with diverse emitters─such as quantum dots, phosphors, and molecular dyes─to amplify emission asymmetry. Building on this foundation, we develop helical-confinement chiroptical superstructures (HCCSs) by stabilizing the confined helical architectures through covalent interactions or in situ polymerization. This approach not only amplifies CPL activity to achieve large dissymmetry factors but also converts fragile helical assemblies into durable architectures. Moreover, the confinement imparts outstanding processability, enabling the resulting materials to be printed, woven, or continuously manufactured, providing sufficient performance for applications within a single chemical framework. In this context, we first introduce the photophysical properties of CPL and the material requirements for practical systems, particularly for intelligent information interaction. We then discuss strategies for CPL generation and amplification, focusing on chiral liquid crystal photonic templates and helical coassembly methods. Subsequently, we highlight the helical-confinement assembly process that produces HCCSs with enhanced processability and scalability. We further showcase how such advances translate into functional applications, ranging from (i) information security and recognition including a multimodal encryption system and high-dimensional optical mapping, (ii) flexible three-dimensional displays and spatial imaging devices, and (iii) imaging and sensing under complex conditions using polarization-differential technologies. Finally, we outline future directions in programmable, scalable, and multifunctional chiral luminescent materials for multidisciplinary applications. We envision that these materials will provide a genetic toolkit of chemical materials to meet application demands and, going forward, will bridge chemistry, materials science, and photonics, paving the way for next-generation optoelectronic devices and systems.

ABSTRACT Helical ladder polymers possess rigid, helically fused backbones that confer distinctive chiroptical properties, yet their integration into polymer brush architectures remains highly challenging. Here, we report the first synthesis of bottlebrush polymers with a helically fused ladder backbone, achieved through acid‐catalyzed intramolecular cyclization followed by controlled ATRP grafting‐from polymerization. By integrating a single‐handed ladder scaffold with flexible, water‐soluble PNIPAM side chains, the resulting architecture markedly enhances the processability and structural tunability of helical ladder polymers. Moreover, the traditional helical ladder, long regarded as completely rigid and static, has been found to exhibit dynamic transition properties. This change was caused by conformational triggering of the thermally driven binaphthyl dihedral angles, which was quantitatively confirmed by the thermodynamic dynamics and molecular dynamics simulations, demonstrating the hierarchy of the transition from axial chirality to helical chirality. Overall, this work establishes a promising synthetic method for helical ladder bottlebrush polymers and demonstrates their potential as versatile platforms for designing dynamic chiral materials.

ABSTRACT Helical ladder polymers possess rigid, helically fused backbones that confer distinctive chiroptical properties, yet their integration into polymer brush architectures remains highly challenging. Here, we report the first synthesis of bottlebrush polymers with a helically fused ladder backbone, achieved through acid‐catalyzed intramolecular cyclization followed by controlled ATRP grafting‐from polymerization. By integrating a single‐handed ladder scaffold with flexible, water‐soluble PNIPAM side chains, the resulting architecture markedly enhances the processability and structural tunability of helical ladder polymers. Moreover, the traditional helical ladder, long regarded as completely rigid and static, has been found to exhibit dynamic transition properties. This change was caused by conformational triggering of the thermally driven binaphthyl dihedral angles, which was quantitatively confirmed by the thermodynamic dynamics and molecular dynamics simulations, demonstrating the hierarchy of the transition from axial chirality to helical chirality. Overall, this work establishes a promising synthetic method for helical ladder bottlebrush polymers and demonstrates their potential as versatile platforms for designing dynamic chiral materials.

All-biomass tunable CPL films based on cellulose nanocrystals and Taxus carbon dots for multimodal anti-counterfeiting and encryption.

In the last decade, boranils have emerged as one of the mostcompetitive candidates among other boron-based dyes due to the ease of their synthesis and postfunctionalization. This review primarily focuses on rational molecular design concepts and postfunctionalization strategies, highlighting the structure-property relationships of boranils to fine-tune their photophysical properties, such as intramolecular charge transfer (ICT), aggregation-induced emission (AIE), circularly polarized luminescence (CPL), and solid-state emission. Overall, the past few decades have witnessed the gradual development of boranil from individual fluorescent molecules to functional building blocks, opening up a wide range of applications in material chemistry, biomedicine, and photocatalysis.

Chiral nanographenes have emerged as promising materials for chiral optoelectronics owing to their intrinsic chiroptical properties. However, their development remains constrained by synthetic challenges, strong π-aggregation, and low fluorescence quantum yields, while emission extending to the near-infrared (NIR) region is still rare. Here, we present a molecular design strategy that combines structural multiplicity with π-extension in a butterfly-shaped fused perylene pentamer scaffold to achieve active circularly polarized luminescence (CPL) emitters. By tuning the Scholl reaction conditions, we selectively obtained either racemic 1a (1a-rac) together with its meso-isomer (1a-meso) or an extended series of nanographenes (1a-1d). X-ray crystallography revealed contorted architectures featuring helicene subunits, while bulky aryl substituents improved solubility, enhanced stability, and enabled enantiomer separation. Owing to their extended π-conjugation, perylene-like frontier orbital distribution, and increased molecular symmetry and rigidity, these nanographenes exhibit highly tunable and remarkable optical and chiroptical properties. Notably, 1a demonstrates outstanding chiroptical performance (Φ F = 65%; B CPL = 66.7 M-1 cm-1), whereas 1d exhibits narrowband emission (FWHM = 37 nm) spanning the far-red to NIR region.

We report the first NHC-catalyzed atroposelective synthesis of axially chiral tetraarylethenes (TAEs) via oxidative desymmetrization of prochiral TAE dialdehydes. This catalytic strategy operates under mild conditions and accommodates a broad range of phenolic and nitrogen nucleophiles, delivering diverse axially chiral TAEs in good yields and up to 99% ee. The method features excellent functional-group tolerance, enables late-stage modification of complex natural products and pharmaceuticals, and is readily scalable. Furthermore, the resulting axially chiral TAEs display distinct photophysical behavior, pronounced aggregation-induced emission (AIE), and strong circularly polarized luminescence (CPL). This work establishes a general and efficient platform for constructing functional chiral TAEs with promising optoelectronic potential.