Chiral organic phosphors with asymmetric electronic configurations and divergent orbital angular momenta are fundamental building blocks for circularly polarized luminescence (CPL) materials, holding great promise for colored LEDs and displays. However, realizing high-purity, high-efficiency white CPL (W-CPL) and circularly polarized long-persistent luminescence (CP-LPL) in a single luminophore remains a formidable challenge. Herein, we report a duplex photopolymerization strategy to construct helical liquid-crystalline charge-trapping chiral architectures, integrating supramolecular cholesteric assembly and in situ olefin photopolymerization. Insulating alkene linkages barely disturb intrinsic singlet-triplet distributions and phosphorescence. Dual covalent/noncovalent crosslinking enhances polymer rigidity, stabilizes triplet excitons, and forms chiral exciplexes to produce high-performance W-CPL from combined fluorescence and phosphorescence. The optimized helical polymer delivers a 0.34 s CP-RTP lifetime, ∼20 s afterglow, 39% quantum efficiency, and giant gp h o s factors (+1.24, -1.40) via charge trapping and chiral light reflection. Chiral FRET further enables yellow/orange/red/NIR CP-LPL. This chiral exciplex polymer resists moisture, solvents, and heat, showing broad application potential in CP-WLEDs and 3D anti-counterfeiting.

Environmentally adaptive circularly polarized photoluminescence and radioluminescence are critical for constructing intelligent optoelectronic devices. However, state-of-the-art chiral organic scintillators are hampered by insufficient circularly polarized luminescence (CPL) dissymmetry, limited wavelength tunability, poor triplet exciton utilization, and compromised stability under harsh operational conditions. Herein, we develop temperature-adaptive chiral diphosphoniums through rational D-A modulation and ionization engineering. Precise conformational regulation affords full-color circularly polarized fluorescence and afterglow across solution, solid, and polymeric states. The resulting helical chiral polymeric liquid crystal (CPLC) films achieve an amplified maximum glum of 0.75 alongside robust anti-quenching, thermal, and radiation resistance. Enabled by efficient intersystem crossing (ISC) and stabilized triplet excitons, the optimized scintillator device delivers superior X-ray imaging ability. Impressively, a cascaded dual-layer reflective architecture further elevates the maximum glum up to 1.8. This work establishes a versatile strategy toward high-performance chiral luminescent platforms for advanced 4D anti-counterfeiting and high-resolution X-ray radiography.

Nonerosive lattice doping of chiral self-assembly is advantageous for applications in polarized optoelectronics, as it evades the packing of molecular rearrangements that preserve the optical activity of microcrystals. However, present chiral microcrystals of phosphine-involved clusters often suffer from low quantum yields and dissymmetry factors (glum) of circularly polarized phosphorescence (CPP), due to limited control over the electromagnetic dipole moment and assembly compatibility of the host and guest. Here, we use chiral diphosphines and trace triphenylphosphines (TPPs) to govern the coordination and nonerosive doping of the binuclear Cu(I) clusters, as demonstrated with a family of heterogeneously doped hexagonal microcrystals based on (R)/(S)-Cu. Green CPP employing one of these pure (R)/(S)-Cu achieves a PLQY and glum of 5.7% and ±0.006, respectively, while the isostructural (R)/(S)-Ag emits similar CPP with lower PLQY (3.5%) and glum values (±0.004), which is caused by excited state deformation and weaker H-bonding. By further preparing crystals through trace doping of TPPs, all crystals feature the same hexagonal morphologies, but phosphorescence enhancement from trace heteroligand-chelated complexes and electronic configurations enables extra triplet populations and decay channels. Thus, the crystals show enhanced PLQYs for red-shifted CPP, as well as better CPL detection (gres = 0.17) and scintillator imaging abilities.

Recently, circularly polarized luminescence (CPL) and room-temperature phosphorescence (RTP) materials have attracted significant attention across various fields. The stereogenic biaryl units are critical sources of CPL and RTP activity, including binaphthyl, binaphthalenediol, and binaphthalenediamine derivatives. However, the stereoselective transformation and chiroptical functionalization of 1,1 '-binaphthyl-2,2 '-diphemyl phosphine (BINAP) and its oxide (BINAPO) are largely unexplored. Herein, a series of axially chiral luminous molecules is prepared by modular covalent-linking of BINAP/BINAPO and arylamine donors (N-phenylcarbazole (CZ) or triphenylamine (TPA)) at 4,4 '-positions to study their photoluminescence and chiroptical properties. Intriguingly, the molecules based on BINAPO emit intense fluorescence, and the persistent RTP of 301-578 ms is achieved when these compounds are doped in the polymer matrixes, which contributes to the formation of the optimized energy gap and intersystem crossing (ISC) by virtue of intramolecular charge transfer (ICT) states and heavier phosphorus atoms. Circular dichroism (CD) spectral studies reveal that all BINAP/ BINAPO derivatives exhibit decent optical activity in dichloromethane (DCM) and weak CPL due to the inferior electro-magnetic transition environment. On the contrary, the co-aggregates, consisting of chiral BINAPO derivatives with helical structures and commercial nematic liquid crystals (N-LCs, 5CB), show significantly enhanced CD and CPL signals with the improved FM value of 0.05-0.10.

While chiral induction and spontaneous symmetry breaking are possibly generated by an achiral compound, it remains a great challenge to rationally predict and control the chirality of a self-assembly process. Herein, we report a chiral hierarchical selfassembly strategy to control and transfer the chirality information using dynamic Schiff-base covalent and coordination chemistry. Triphenylamine (TPA) atropisomers are used to form the prochiral [2+3] metal-cages (Co-TPA, Ni-TPA, and Zn-TPA), which exhibit the P or M chiral conformation. Leveraging the coordination-directed enantioselectivity between the chiral auxiliary ligands and vacant metal sites, the remote stereochemistry information can be successfully transferred from chiral BNP to the TPA motif of the metal-cage, facilitating optical activity and circularly polarized luminescence with red color. When the dialdehyde precursor was further modified by embedding a pyridyl unit as an additional coordination site, the disperse cages could be connected into one mesomeric Cd-1D cage-metal-organic frameworks (cage-MOF) and a pair of enantiomeric Zn-2D layered cage-MOFs through the chirality transfer pathways in different dimensions. Notably, spontaneous symmetry breaking and chiral self-sorting of conglomerate crystallization can be achieved for (P)-Zn-2D and (M)-Zn-2D. Furthermore, the enantiomeric enrichment of (P)/(M)-Zn-2D microcrystals with controlled handedness is accomplished by the induced self-seeding crystal and stirring during the self-assembly process.

Renewable electricity-driven capture and conversion of oceanic dissolved inorganic carbon into value-added chemicals offers a sustainable route towards negative carbon emissions and a circular carbon economy. Here we present an artificial ocean carbon recycling system that captures and converts oceanic carbon sources into biochemicals through a decoupled electro-biocatalytic hybrid process. The system captures CO2 from natural seawater under very dilute yet realistic dissolved inorganic carbon conditions (2.16 mM) with high capture efficiency (>70 Tandem electro-biocatalytic systems present a versatile platform for producing a variety of synthetic products using CO2 as a starting material. Here direct ocean carbon capture is incorporated into an electrolysis scheme to produce formic acid from CO2 dissolved in seawater that is subsequently converted to succinate in a bioreactor.

Disperse dyes having pyridine-2,6-dione based coupling components often suffer from deteriorated uniformity in the fiber-dyeing processes due to pH-induced azo-hydrazone tautomerism. To overcome this deficiency, the functional group transformation (FGT) strategy was employed to convert the cyano group of one pyridine-2,6-dione derivative to a less electron-withdrawing amide group or even a hydrogen atom, so as to hinder the transformation from the hydrazone form to deprotonated azo form, and hence improve the acid-base stability of the target dyes. As a result, six new hydrazone dyes were synthesized with strong acid-base stability, which can be confirmed by related UV-Vis spectra. Reduced charge delocalization in the modified dyes, weakened molecular polarization, and increased energy barrier for the intramolecular transfer of the hydrazone proton were believed to play important roles in the fixation of hydrazone configuration for the new dyes. Detailed theoretical calculations further demonstrated the increased conversion energy barriers. The X-ray crystal structure analysis revealed that the decyano pyridine-2,6-dione dyes contain denser fused six-membered intramolecular hydrogen-bonding rings, and the hydrogen bond lengths are significantly shorter than those in previously reported pyridine-2,6-dione based dyes, which further stabilize the hydrazone protons of dyes in this work. The fundamental FGT strategy elucidated in this study is suggested to be helpful in the improvement of dyeing performance for a wide variety of existing hydrazone dyes.

Phosphorus-based luminescent materials consist of certain phosphorus in the aromatic backbones, endowing a larger nuclear charge (Z, 15P), rich valence states for the phosphorus core, and various electron geometries. These features enable promising exploitation for luminescent materials with significant quantum efficiencies and tunable singlet and triplet populations. This mini review focuses on the break-throughs of organic and organometallic phosphorus compounds in advanced circularly polarized fluorescence (CPF) and circularly polarized room-temperature phosphorescence (CP-RTP) by unveiling the structure-function relationships, e.g., design concept, charge transfer (CT) type, chiral conformation, and excited state transition configuration, and the recent applications in optical information encryption, lighting-displaying, and organic light emitting diodes (OLEDs). By dedicated analysis of current progresses, we hope this work will throw insights into phosphorus-based CPF and CP-RTP behaviors and provide a reference for the rational design of high-performance phosphorus-based emitters.

Commercial phosphines and phosphoniums were commonly reported to have unstable triplet dissipation because of the flexible C-P pyramidal geometry, resulting in extremely weak or no phosphorescence. To boost triplet populations and stability by restricting the molecular motion and rebuilding the electronic structures, we reported that the dual-ring-locking strategy could enable elevated intersystem crossing (ISC) and triplet radiation for the rigid benzo[b]phospholium configuration, exhibiting intense persistent room temperature phosphorescence (RTP) in poly(vinyl alcohol) (PVA). Among them, dual-ring-locked [P1]+[Cl]- showed near-ultraviolet fluorescence maximized at 400 nm in dichloromethane and blue RTP emission at 453 nm (Φphos ≈ 12.4%, τphos > 1200 ms) in the PVA matrix. In contrast, [P2]+[Cl]- possessed a single ring-locked nucleus that had red-shifted emission and weak phosphorescence (Φphos < 1.8%, τphos = 74.2 ms). Time-dependent density functional theory (TD-DFT) disclosed that the improved spin-flipping of phosphoniums benefited from the integrated π-π*/n-π* transition, rational split energy, and rigid excited states. The impressive OU-RTP duration could function as an afterglow pattern for optical encryption or as an emitting layer for light-emitting diode (LED) applications.

The potential of chiral organic molecules exhibiting circularly polarized luminescence (CPL) for practical applications hinges on the luminescence efficiency and dissymmetry factor (glum). However, surpassing the molecular limitations of dissymmetry factors remains a significant challenge, primarily due to the different parity selection rules governing the electric and magnetic dipole moments in chiral molecules. In this study, we tackle this inherent constraint by designing a triplet sensitization photon upconversion system using nontoxic CuInS2 quantum dots (QDs) photosensitizer. We demonstrate a 43-fold amplification of CPL in QD-sensitized triplet fusion process compared to the direct photoexcitation. Notably, a high green-to-blue upconversion quantum efficiency of 12.7 ± 0.19% (normalized to 100%) was achieved. The dissymmetry factors of QD-sensitized upconversion CPL outperform previous reports based on molecular photosensitizers. The observed large glum, according to our modeling and first-principles calculations, originates from the unique structural rearrangement of the chiral emitter during the ultrafast triplet energy transfer process. Our work provides a new strategy and mechanistic insights for CPL amplification through triplet sensitization.

Due to the circularly polarized luminescence (CPL) and high efficiency, chiral phosphorescent complex holds promise for CP organic light-emitting diode (CP-OLED) and 3D display, but the application of chiral manganese(II) (Mn(II)) complex is rare. Herein, the CP-OLEDs with Mn(II) enantiomers, R/S-DFPO-MnBr2 and R/S-XTDPO-MnBr2, based on tert-butyl(6-(diphenylphosphoryl) dibenzo[b,d]furan-4-yl)(phenyl)phosphine oxide and tert-butyl(5-(diphenylphosphoryl)-9,9-dimethyl-9H-xanthen-4-yl)(phenyl) phosphine oxide ligands are reported containing phosphorus-centered point chirality. R/S-DFPO-MnBr2 and R/S-XTDPO-MnBr2 exhibit yellow-green emissions peaking at 541 and 532 nm with photoluminescence quantum yields of up to 87%, CPL spectra with dissymmetry factors (|gPL|) around 2.0 x 10-3. The CP-OLEDs achieve external quantum efficiencies of up to 12.9% and CP electroluminescence spectra with |gEL| values of about 1.8 x 10(-)3, suggesting potential application of chiral Mn(II) complexes.

Due to the conformational stability and straightforward synthesis, centrally chiral organic small molecules serve as ideal candidates for constructing multi-resonance thermally activated delayed fluorescence (CP-MR-TADF) materials, exhibiting circularly polarized luminescence (CPL) properties. However, the advancement of CP-MR-TADF materials exhibiting point chirality remains restricted primarily to carbon-based chiral compounds, and the sulfur-centered structures are very few. Herein, we report the synthesis of six pairs of sulfur-centered CP-MR-TADF enantiomers, achieved by covalently fusing N-substituted sulfoximine fragments featuring sulfur stereocenters to a widely used multiple resonance parent core. These novel CP-MR-TADF materials demonstrate blue-green or green emission peaking at 495–509 nm with narrow full widths at half maximum of less than 30 nm, small singlet-triplet energy gaps of down to 0.03 eV and high photoluminescence quantum yields of up to 92.8

Overcoming spin-forbidden radiation in chiral phosphors has attracted enormous attention because of their capacity to exhibit circularly polarized organic ultra-long room temperature phosphorescence (CP-OURTP). However, their development has been hindered by the short lifetimes and low dissymmetry factors, which are attributed to the differing parity selection rules that govern the electric and magnetic dipole moments in chiral molecules and poor triplet populations via intersystem crossing (ISC). Considering stepwise chiral amplification at molecular and supramolecular aspects, herein, we first reported donor-decorated BINAPs/BINAPOs with tunable D-A character and triplet incubation, which could enable hybridized local and charge-transfer (HLCT) characteristics, heavy atoms, and p-π* effects. These emitters could serve as guests in the polymer matrix. The doped phosphorescent polymer exhibits unimolecular circularly polarized luminescence (C) with high quantum efficiency, impressive CP-OURTP lifetimes (up to 1.02 s), and decent dissymmetry factors (10-3 level). Comprehensive studies unveil that the impressive CP-OURTP from monomer emission is ascribed to the 1HLCT-controlled ISC, long-lived 3LE-governing triplet radiation, and superior electric-magnetic dipole moment environments. Moreover, given the high RTP activity of rigid polymerization, we demonstrate their potential application in CP-OURTP amplification. Using in situ chiral liquid crystal polymerization, RM257 liquid crystals doped with 0.1-1.0 wt% PO1 guests demonstrate a secondary helical assembly, showing an amplified g CP-RTP factor (±0.11) and a long lifetime (0.83 s) after photopolymerization. The current materials' excellent performance in CP-OURTP and structural dependence could lead to their use in afterglow patterns for multiple optical encryption.

Transformation of the electronic spin states has received significant interest in recent years because of its applications in the magnetic information storage materials and optical response switches. However, it can be formidably challenging to use ultraviolet (UV) light as a contactless stimulus to alter the electronic spin states of the supramolecular cages. Inspired by the approach on the radical cation mechanism of the Scholl reaction and the photocyclization reactivity of tetraphenylethylene (TPE) derivatives, we report two photochromic cages (cage-TPE-1 and cage-TPE-2) that can be photochemically transformed from electron paramagnetic resonance (EPR)-silent to EPR-active form via UV irradiation due to the photo-induced electron transfer process at the TPE moiety. EPR provided a strong single-electron signal with a g value of 2.003 in cage-TPE-1 and cage-TPE-2 but no signal was detected for the pristine samples without the UVexposure. The transformation can be monitored by ultraviolet–visible–near-infrared (UV–vis–NIR) and photoluminescence (PL) spectroscopy. The photogenic radical cage intermediate was unstable in solution resulting in the degradation and intramolecular cyclization of the reactive species, while the radicals were found to be stable and persistent in the solid state due to the spin delocalization, the steric protection of confined cavities, and the oxygen isolation. Both theoretical calculations and spectral measurements suggest that the photogenic radical cage-TPE-2(•+) experiences photocyclization on the TPE core. Compared with the close-shell cage, the radical cage-TPE-1(•+) and cage-TPE-2(•+) exhibit better photothermal conversion performance due to the incubated infrared absorption from open-shell electron feature and reduced band gap.

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising for high-definition organic light-emitting diodes (OLEDs) due to their high exciton utilization and color purity. However, strong interchromophore interactions cause most MR-TADF emitters with planar structures to aggregate at high doping concentrations, leading to degraded efficiencies. Herein, using benzenesulfonyl-functionalized dibenzothiophene sulfoximine with steric effects, three MR-TADF emitters (2SBN, 3SBN, and 4SBN) are synthesized by coupling the classic DtBuCzB skeleton at different sites. Three emitters exhibit green or blue-green emission with full width at half maximum (FWHM) values less than 29 nm and photoluminescence quantum yields exceeding 90%. OLEDs based on 2SBN, 3SBN, and 4SBN achieve high maximum external quantum efficiency (EQEmax) values of 30.1%, 27%, and 33.8%, respectively, at a 5 wt.% doping concentration. Notably, due to the distorted conformation of 4SBN and suppressed intermolecular interaction, the OLED remains high EQEmax of 28.9% at a doping concentration of 20 wt.%. These results demonstrate the feasibility of molecular design to modulate spatial conformations via positional isomerism to develop MR-TADF emitters with reduced concentration quenching. Three efficient multiple resonance thermally activated delayed fluorescence emitters are synthesized through positional isomerization of benzenesulfonyl-functionalized dibenzothiophene sulfinylimide units. The corresponding organic light-emitting diodes show high external quantum efficiencies (EQEmax) of up to 33.8%. Even at a doping concentration of 20 wt.%, the EQEmax remains at 28.9%. image

Polar cyano fragments and their isomeric isocyano counterparts have attracted great attention as stimuli-responsive luminescent materials in a wide range of fields including organic light-emitting diode devices, chemical fluorescent sensors, photoelectric semiconductors, anti-counterfeit products, etc., mainly because of their typical electron-deficient activity, noncovalent recognition ability, and variable coordination capacity. The electron-deficient and polar nature of these blocks have significant effects on the properties of the cyano/isocyano-based luminophore materials, especially concerning their condensed state-dependent electronic structures. Among them, donor-acceptor (D-A) derived unimolecular and co-assembled luminophores have attracted more attention because their large delocalized structures and noncovalent interaction recognition sites can rebuild the electronic transfer character in the aggregative state, thus endowing them with outstanding stimuli-responsive luminescent behavior via intermolecular and intramolecular charge transfer in polytropic morphologies. In this perspective paper, we give a brief introduction on stimuli-responsive organic and coordinated luminophores and the documented typical design concepts and applications in recent years. It is expected that this perspective article will not only summarize the recent developments of polar cyano/isocyano-derived luminophores and their coordination compounds via structural tailoring and self-assembly but also throw light on the future of the design of more sophisticated stimuli-responsive architectures and their versatile properties.

Organic phosphors integrating circularly polarized persistent luminescence (CPPL) across the visible range are widespread for applications in optical information encryption, bioimaging, and 3D display, but the pursuit of color-tunable CPPL in single-component organics remains a formidable task. Herein, via in situ photoimplanting radical ion pairing into axial chiral crystals, we present and elucidate an unprecedented double-module decay strategy to achieve a colorful CPPL through a combination of stable triplet emission from neutral diphosphine and doublet radiance from photogenic radicals in an exclusive crystalline framework. Owing to the photoactivation-dependent doublet radiance component and an inherent triplet phosphorescence in the asymmetric environment, the CPL vision can be regulated by altering the photoactivation and observation time window, allowing colorful glow tuning from blue and orange to delayed green emission. Mechanism studies clearly reveal that this asymmetric electron migration environment and hybrid n-pi* and pi-pi* instincts are responsible for the afterglow and radical radiance at ambient conditions. Moreover, we demonstrate the applications of colorful CPPL for displays and encryption via manipulation of both excitation and observation times.

Color filters play an important role in the quality of complementary metal-oxide-semiconductors and thin-filmtransistor liquid-crystal displays. Although pigment nanoparticles have traditionally been used as color filter colorants, the use of molecular dyes for preparing high-quality color filters is an emerging strategy. However, few studies have investigated the relation between the structure of dyes and their color filter characteristics, such as solubility, and thermal stability and photostability. In this study, six phthalocyanine dyes with different branched substituents and central metals (zinc and copper) were developed. These dyes displayed high levels of solubility in propylene glycol monomethyl ether acetate (up to 40.8 wt%), high light transmission, and satisfactory thermal stability and photostability, indicating their potential application in color filters. They may provide a way to explore more molecular dyes for color filters with excellent dissolution properties.

The design and construction of chiral phosphors with significant long-lived triplet exciton decay have received great attention because of their prospective applications in ultra-long circularly polarized roomtemperature phosphorescence (CP-RTP) for chiral optics. However, the practical utilization of pure organics as triplet incubators is often hindered by their spin-forbidden transition. Therefore, it is a substantial challenge for the developments of organic-derived CPRTP emitters with both long lifetimes and asymmetry factors. Herein, via precisely manipulating hybridized local and charge transfer (HLCT) and multiple n−π* effects, we report the first P,N-embedded tactic to construct the BINAP-derived emitters, which show tunable circularly polarized luminescence (CPL) with near-unity photoluminescence quantum efficiency (PLQY = 95.3%), |glum| values (1.2 to 6.2 × 10−3), and ultra-long RTP with remarkable lifetime as long as 448 ms in the polymethyl methacrylate. Experiments and quantum chemistry simulations unveil that the abovementioned triplet decay is derived from tunable HLCT and a balanced electric-magnetic dipole moment environment. Moreover, the synergetic enhancement of chemical and configurational stability enables stable chiral diradicals with a high diradical character (y0 = 0.953) and near-infrared ray (NIR) optical activity. This work provides important clues for CP-RTP phosphors and chiral diradical materials.

Molecular topology synthesis of polycyclic aromatic heterocycles (PAHs) with diradical character takes root in the intramolecular coupling breakthrough. Herein, we report selectively Mn(III)/Cu(II)-mediated C−P and C−H bond cleavage to obtain robust donorfused phosphoniums with helical or planar geometries and distinct cationic charges. The former helical structures incorporate a common phospha[5]helication acceptor and different arylamines donors, and the latter planar one contains a phospha[6]dication and the same donors. These unprecedented donor-acceptor (D−A) pairs show unique topology-dependent optoelectronic properties. The folded helical radical centers possess an extreme electron-deficient state and throughspace isolation with high diradical character (y0 = 0.989). Moreover, the ingenious charge transfer (CT) and locally excited (LE) transition components facilitate diverse hybridized local and charge transfer (HLCT) in different solvents, endowing the highest emission bandgap variation of 0.78 eV (~217 nm). The cationic emission could also be adjusted from blue to near-infrared regions via topology tailoring and polardependent HLCT, which could output additional circularly polarized luminescence in a compatible chiral menthol matrix with elevated quantum efficiency and retained deep-red glow. It is worth mentioning that an atomically precise Mn(III) halide has been unprecedentedly captured and determined for the C−P bond activation