Helical β-isoindigo-Based Chromophores with B−O−B Bridge: Facile Synthesis and Tunable Near-Infrared Circularly Polarized Luminescence

It is essential to create organic compounds that exhibit circularly polarized luminescence (CPL) in the near-infrared (NIR) range. Helicene-type emitters possess appealing chiroptical features, however, such NIR molecules are scarce due to a paucity of synthetic strategies. Herein, we developed a series of helical β-isoindigo-based B−O−B bridged aza-BODIPY analogs that were synthesized conveniently. The reaction of diimino-β-isoindigo with a heteroaromatic amine produced a restricted ligand cavity, which triggered off the generation of a B−O−B bridge. The B−O−B bridge led to distorted conformations that satisfy the helical requirements, resulting in excellent spectroscopic and chiroptical properties. Tunable CPL with the highest luminescence dissymmetry factor (g_lum) of 1.3×10⁻³ and a CPL brightness (B_CPL=11.5 M⁻¹ cm⁻¹) in the NIR region was achieved. This synthetic approach is expected to offer a new opportunity to chiral chemistry and increase flexibility for chiroptical tuning.     

Synthesis of Highly Luminescent Chiral Nanographene

Chiral nanographenes with both high fluorescence quantum yields (Φ_F) and large dissymmetry factors (g_lum) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement of g_lum, whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with high Φ_F by helical π-extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record high Φ_F of 93 % among the reported chiral nanographenes and excellent CPL brightness (B_CPL) of 32 M⁻¹ cm⁻¹.     

Solvation-Mediated Self-Assembly from Crystals to Helices of Protic Acyclic Carbene AuI-Enantiomers with Chirality Amplification

Constructing chiral supramolecular assembly and exploring the underlying mechanism are of great significance in promoting the development of circularly polarized luminescence (CPL)-active materials. Herein, we report a solvation-mediated self-assembly from single-crystals to helical nanofibers based on the first protic acyclic (methoxy)(amino)carbenes (pAMACs) Au^I-enantiomers driven by a synergetic aurophilic interactions and H-bonds. Their aggregation-dependent thermally activated delayed fluorescence properties with high quantum yields (Φ_FL) up to 95 % were proved to be attributed to packing modes of Au⋅⋅⋅Au dimers with π-stacking or one-dimensional extended Au⋅⋅⋅Au chains. Via drop-casting method, supramolecular P- or M-helices were prepared. Detailed studies on the helices demonstrate that formations of extended helical Au⋅⋅⋅Au molecular chains amplify supramolecular chirality, leading to strong CPL with high dissymmetry factor (|g_lum|=0.030, Φ_FL=67 %) and high CPL brightness (B_CPL) of 4.87×10⁻³. Our findings bring new insights into the fabrication of helical structures to improve CPL performance by modifying aurophilic interactions.     

Luminescent Chiral Exciplexes with Sky-Blue and Green Circularly Polarized-Thermally Activated Delayed Fluorescence

Luminescent exciplexes based on a chiral electron donor and achiral acceptors are reported as a new approach to design circularly polarized (CP) and thermally activated delayed fluorescence (TADF) emitters. This strategy results in rather high CP luminescence (CPL) values with g_lum up to 7×10⁻³, one order of magnitude higher in comparison to the CPL signal recorded for the chiral donor alone (g_lum ∼7×10⁻⁴). This increase occurs concomitantly with a CPL sign inversion, as a result of the strong charge-transfer emission character, as experimentally and theoretically rationalized by using a covalent chiral donor-acceptor model. Interestingly, blue, green-yellow and red chiral luminescent exciplexes can be obtained by modifying with the electron accepting character of the achiral unit while keeping the same chiral donor unit. These results bring new (inter)molecular guidelines to obtain simply and efficiently multi-color CP-TADF emitters.     

Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness

Chiral macrocyclic dimers, trimers, and tetramers composed of paraphenylene and tethered binaphthyl were synthesized, and their molecular structures and chiroptical properties were investigated. X-ray analysis and theoretical calculations revealed that multiple twisted molecular structures – dimers, trimers, and tetramers – adopt figure-of-eight, Möbius triangle, and concave rectangle structures, respectively. These homologues have large ϵ values in their UV-vis absorption spectra because of the π-conjugation of the naphthalene-phenylene-naphthalene frameworks. Owing to the shape-persistent ring structure and tethering with −OCH₂CH₂O−, high fluorescence quantum yields and a relatively high dissymmetry factor g_CPL in circularly polarized luminescence (CPL) spectra were achieved. This results in CPL brightness (B_CPL) of over 100, which is greater than that of the conventional organic CPL dye.     

Enhanced Circularly Polarized Luminescence from Reorganized Chiral Emitters on the Skeleton of a Zeolitic Imidazolate Framework

A chiral zeolitic imidazolate framework (ZIF) showing circularly polarized luminescence (CPL) has been successfully constructed by blending binapthyl‐derived chiral emitters with ZIF‐8 rhombic dodecahedron nanoparticles. This approach solves a major trade‐off in CPL‐active materials: the large luminescence dissymmetry factor (g_lum) always suffers from suppression of luminescence efficiency. Compared to the optical properties of chiral emitters, the obtained chiral ZIF nanomaterials showed an enhanced fluorescence efficiency while the |g_lum| value is significantly amplified by one order of magnitude. Additionally, enantioselective fluorescence sensing in response to α‐hydroxycarboxylic acids has been enhanced in chiral ZIFs. Reorganization and conjunction of chiral emitters to the skeleton of ZIF nanoparticles can greatly improve both the luminescence quantum yield and circularly polarization, which facilitates the design of more efficient chiroptical materials.     

Yellow Circularly Polarized Luminescence from C1‐Symmetrical Copper(I) Complexes

The synthesis of chiral C₁‐symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |g_lum|=1.2×10^?3. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL‐emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.     

Enhancing Circularly Polarized Phosphorescence via Integrated Top-Down and Bottom-Up Approach

In the dynamic domain of chiroptical technologies, it is imperative to engineer emitters endowed with circularly polarized luminescence (CPL) properties. This research demonstrates an advancement by employing a combined top-down and bottom-up strategy for the simultaneous amplification of photoluminescence quantum yield (Φ) and the luminescence dissymmetry factor (g_lum). Square-planar Pt(II) complexes form helical assemblies, driven by torsional strain induced by bis(nonyl) chains. Integration of chiral anions leads these assemblies to prefer distinct helical sense. This arrangement activates the metal-metal-to-ligand charge transfer (MMLCT) transition that is CPL-active, with Φ and |g_lum| observing an upswing contingent on the charge number and aryl substituents in chiral anions. Utilizing the soft-lithographic micromolding in capillaries technique, we could fabricate exquisitely-ordered, one-dimensional co-assemblies to achieve the metrics to Φ of 0.32 and |g_lum| of 0.13. Finally, our spectroscopic research elucidates the underlying mechanism for the dual amplification, making a significant stride in the advancement of CPL-active emitters.     

Yellow Circularly Polarized Luminescence from C1-Symmetrical Copper(I) Complexes

The synthesis of chiral C₁-symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |g_lum|=1.2×10⁻³. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL-emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.     

Integrating Achiral and Chiral Organic Ligands in Zero-Dimensional Hybrid Metal Halides to Boost Circularly Polarized Luminescence

Chiral zero-dimensional hybrid metal halides (0D HMHs) could combine excellent optical properties and chirality, making them promising for circularly polarized luminescence (CPL). However, chiral 0D HMHs with efficient CPL have been rarely reported. Here, we propose an efficient strategy to achieve simultaneously high photoluminescence quantum yield (PLQY) and large dissymmetry factor (g_lum), by integrating achiral and chiral ligands into 0D HMHs. Specifically, three pairs of chiral 0D hybrid indium-antimony chlorides are synthesized by combing achiral guanidine with three types of chiral methylbenzylammonium-based derivatives as the organic cations. These chiral 0D HMHs exhibit near-unity PLQY and large g_lum values up to around ±1×10⁻². The achiral guanidine ligand is not only essential to crystallize these hybrid indium-antimony chlorides to achieve near-unity PLQYs, but also greatly enhances the chirality induction from organic ligands to inorganic units in these 0D HMHs. Furthermore, the choice of different chiral ligands can modify the strength of hydrogen bonding interactions in these 0D HMHs, to maximize their g_lum values. Overall, this study provides a robust way to realize efficient CPL in chiral HMHs, expanding their applications in chiroptical fields.     

Amplified circularly polarized luminescence enabled by photon upconversion in spin-coating cellulose matrix

It is of great significance to construct organic circularly polarized luminescence systems (CPL) with large luminescence dissymmetry factors (g_lum) for practical applications. Here we report organic CPL systems constructed by merging triplet-triplet annihilation upconversion chromophores in cellulose matrices. The chirality of the matrix is transferred to the achiral chromophores of photon upconversion and then the multistep energy transfer processes of upconversion amplify g_lum. The g_lum value of upconversion CPL in the left-handed ethyl cellulose and the right-handed (acetyl) ethyl cellulose are up to +0.1 and ?0.15, respectively. The study provides a straightforward approach for constructing solid organic upconversion CPL materials with large g_lum, which may expand the application potentials of organic chiroptical materials.     

TADF-Sensitized Fluorescent Enantiomers: A New Strategy for High-Efficiency Circularly Polarized Electroluminescence**

A promising strategy of thermally activated delayed fluorescence (TADF) sensitized circularly polarized luminescence (CPL) has been proposed for improving the electroluminescence efficiencies of circularly polarized fluorescent emitters. Compared with chiral TADF emitters which suffer from the dilemma of small ΔE_ST accompanied by small k_r, the TADF-sensitized CPL (TSCP) strategy using TADF molecules as sensitizers and CP-FL molecules as emitters might be the most promising method to construct high-performance circularly polarized organic light-emitting diodes (CP-OLEDs). Consequently, by taking advantage of the theoretically 100 % exciton utilization of TADF sensitizers, especially, by designing CP-FL emitters with high PLQY, narrow FWHM and large g_lum values, TSCP-type CP-OLEDs with excellent overall performances can be realized.     

Enhanced Circularly Polarized Luminescence in Emissive Charge‐Transfer Complexes

Achieving a large dissymmetry factor (g_lum) is a challenge in the field of circularly polarized luminescence (CPL). A chiral charge‐transfer (CT) system consisting of chiral electron donor and achiral electron acceptor shows bright circularly polarized emission with large g_lum value. The chiral emissive CT complexes could be fabricated through various approaches, such as grinding, crystallization, spin coating, and gelatinization, by simply blending chiral donor and achiral acceptor. The structural synergy originating from π–π stacking and strong CT interactions resulted in the long‐range ordered self‐assembly, enabling the formation of supramolecular gels. Benefiting from the large magnetic dipole transition moment in the CT state, the CPL activity of CT complexes exhibited large circular polarization. Our design strategy of the chiral emissive CT complexes is expected to help the development of new molecular engineering strategies for designing highly efficient CPL‐active materials.     

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead-free Hybrid Metal Halides

Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor (g_lum) is difficult due to usually unmatched electric transition dipole moment (μ) and magnetic transition dipole moment (m) of materials. Herein we tackle this issue by playing a “cascade cationic insertion” trick to achieve strong CPL (with PLQY of ~100 %) in lead-free metal halides with high g_lum values reaching −2.3×10⁻² without using any chiral inducers. Achiral solvents of hydrochloric acid (HCl) and N, N-dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting the perovskite structure to induce the “intrinsic” chirality. Surprisingly, additional insertion of Cs⁺ cation to substitute partial (CH₃)₂NH₂⁺ transforms the chiral space group to achiral but the crystal maintains chiroptical activity. Further doping of Sb³⁺ stimulates strong photoluminescence as a result of self-trapped excitons (STEs) formation without disturbing the crystal framework. The chiral perovskites of indium-antimony chlorides embedded on LEDs chips demonstrate promising potential as CPL emitters. Our work presents rare cases of chiroptical activity of highly luminescent perovskites from only achiral building blocks via spontaneous resolution as a result of symmetry breaking.     

Achiral Dichroic Dyes-mediated Circularly Polarized Emission Regulated by Orientational Order Parameter through Cholesteric Liquid Crystals

It is noteworthy that cholesteric liquid crystal (CLC) platforms have been witnessed in high-performance circularly polarized luminescence (CPL) behaviors through the highly organized chiral co-assembled arrangement of achiral dyes. However, most CPL-active design strategies are closely relative to the helix co-assembly structure of CLC rather than achiral dyes. Herein, we developed an intriguing regulation strategy for CPL-active CLC materials. They were regulated using the orientational order parameter (S_F) of achiral dichroic dyes as an incisive probe for the order arrangement degree of achiral dyes in CLC media. The I-shaped phenothiazine derivative PHECN dye (S_F=0.30) emitted a strong CPL signal (|g_lum|=0.47). In contrast, the T-shaped derivative (PHEBen) dye (S_F=0.09) showed a weak circular polarization level (|g_lum|=0.07) at similar CLC textures. Most interestingly, this kind of dichroic PHECN dye with a higher S_F could greatly improve the contrast ratio of CPL (Δg_lum=0.47) and emission intensity (ΔFL=46.0 %) at direct-current electric field compared with the T-shaped PHEBen (Δg_lum=0.07 and ΔFL=1.0 %) in CLC. This work demonstrates that an induced CPL emission can be mediated using achiral dichroic dye, which will open a new avenue for developing excellent CPL-active display materials.     

Highly Strained Oxygen-Doped Chiral Molecular Belts of the Zigzag-Type with Strong Circularly Polarized Luminescence

Herein we report a two-directional cyclization strategy for the synthesis of highly strained depth-expanded oxygen-doped chiral molecular belts of the zigzag-type. From the easily accessible resorcin[4]arenes, an unprecedented cyclization cascade generating fused 2,3-dihydro-1H-phenalenes has been developed to access expanded molecular belts. Stitching up the fjords through intramolecular nucleophilic aromatic substitution and ring-closing olefin metathesis reactions furnished a highly strained O-doped C₂-symmetric belt. The enantiomers of the acquired compounds exhibited excellent chiroptical properties. The calculated parallelly aligned electric ( μ ) and magnetic ( m ) transition dipole moments are translated to the high dissymmetry factor (|g_lum| up to 0.022). This study provides not only an appealing and useful strategy for the synthesis of strained molecular belts but also a new paradigm for the fabrication of belt-derived chiroptical materials with high CPL activities.     

Chiroptical Amplification of Induced Circularly Polarized Luminescence in Nucleotide-Templated Supramolecular Polymer

Efficient circularly polarized luminescence (CPL) from purely organic molecules holds great promise for applications in displays, sensing, and bioimaging. However, achieving high dissymmetry values (g_lum) from organic chromophores remains a significant challenge. Herein, we present a bioinspired approach using adenosine triphosphate (ATP)-triggered supramolecular polymerization of a naphthalene diimide-derived monomer ( ANSG ) to induce CPL with a remarkable g_lum value of 1.1×10⁻². The ANSG molecules undergo a templated, chiral self-assembly through a cooperative growth mechanism in the presence of ATP, resulting in scrolled nanotubes with aggregation-induced enhanced emission (AIEE) and induced CPL. Furthermore, we demonstrate the concept of chiroptical amplification of induced CPL by efficiently amplifying asymmetry using a mixture of chiral ATP and achiral pyrophosphate. This innovative approach opens numerous opportunities in the emerging field of circularly polarized luminescence.     

Aggregation-Induced Circularly Polarized Luminescence from Boron Complexes with a Carbazolyl Schiff Base

A variety of carbazolyl-appended Schiff bases were readily synthesized from 1-formylcarbazoles and aniline derivatives. Boron complexation of the resulting ligands allowed for facile preparation of new carbazole-based BODIPY analogues showing solid-state fluorescence. Furthermore, some dyes were converted into chiral compounds through the Et₂AlCl-mediated incorporation of a binaphthyl unit. The chiral dyes showed aggregation-induced fluorescence and circularly polarized luminescence (CPL) with the Φ_F and g_lum of up to 0.22 and −3.5×10⁻³, respectively, in the solid state. The solid-state fluorescence and CPL were well characterized by the crystal packing analyses and DFT calculations.     

Circularly Polarized Luminescence from Axially Chiral BODIPY DYEmers: An Experimental and Computational Study

With our new home‐built circularly polarized luminescence (CPL) instrument, we measured fluorescence and CPL spectra of the enantiomeric pairs of two quasi‐isomeric BODIPY DYEmers 1 and 2 , endowed with axial chirality. The electronic circular dichroism (ECD) and CPL spectra of these atropisomeric dimers are dominated by the exciton coupling between the main π–π* transitions (550–560 nm) of the two BODIPY rings. Compound 1 has strong ECD and CPL spectra (g_lum=4×10^?3) well reproduced by TD‐DFT and SCS‐CC2 (spin‐component scaled second‐order approximate coupled‐cluster) calculations using DFT‐optimized ground‐ and excited‐state structures. Compound 2 has weaker ECD and CPL spectra (g_lum=4×10^?4), partly due to the mutual cancellation of electric–electric and electric–magnetic exciton couplings, and partly to its conformational freedom. This compound is computationally very challenging. Starting from the optimized excited‐state geometries, we predicted the wrong sign for the CPL band of 2 using TD‐DFT with the most recommended hybrid and range‐separated functionals, whereas SCS‐CC2 or a DFT functional with full exact exchange provided the correct sign.