Circularly Polarized Luminescence Emission Research Articles

Upconversion/Downshifting Circularly Polarized Luminescence over 1200 nm in a Single Nanoparticle for Optical Anticounterfeiting and Information Encryption.

Multimodal upconversion and downshifting circularly polarized luminescent materials hold significant potential for optical anticounterfeiting applications due to their exceptional chiroptical properties. However, constructing these materials within a single emitter remains challenging. In this study, a conceptual model of multimodal up-conversion/downshifting circularly polarized luminescence (CPL) is realized within a single nanoparticle. A new type of nanoparticles with multilayer core-shell architecture is fabricated, capable of delivering upconversion/downshifting luminescence, when excited by a 980 nm laser. Utilizing a co-assembly strategy, multimodal upconversion/downshifting CPL emission, covering a broad emission range from ultraviolet (UV) to the second near-infrared (NIR-II) region, can be realized at the supramolecular level. These chiroptical properties closely follow the chirality of host matrix and are strongly dependent on the distribution mode of nanoparticles within the matrix films. The multimodal upconversion/downshifting CPL behavior enabled cutting-edge encryption applications including optical anticounterfeiting and information encryption. This work introduces a novel approach to designing multimodal upconversion/downshifting CPL materials and opens new avenues for the development of chiroptical functional materials.

Upconversion/Downshifting Circularly Polarized Luminescence over 1200 nm in a Single Nanoparticle for Optical Anticounterfeiting and Information Encryption

Multimodal upconversion and downshifting circularly polarized luminescent materials hold significant potential for optical anticounterfeiting applications due to their exceptional chiroptical properties. However, constructing these materials within a single emitter remains challenging. In this study, a conceptual model of multimodal up‐conversion/downshifting circularly polarized luminescence (CPL) is realized within a single nanoparticle. A new type of nanoparticles with multilayer core‐shell architecture is fabricated, capable of delivering upconversion/downshifting luminescence, when excited by a 980 nm laser. Utilizing a co‐assembly strategy, multimodal upconversion/downshifting CPL emission, covering a broad emission range from ultraviolet (UV) to the second near‐infrared (NIR‐II) region, can be realized at the supramolecular level. These chiroptical properties closely follow the chirality of host matrix and are strongly dependent on the distribution mode of nanoparticles within the matrix films. The multimodal upconversion/downshifting CPL behavior enabled cutting‐edge encryption applications including optical anticounterfeiting and information encryption. This work introduces a novel approach to designing multimodal upconversion/downshifting CPL materials and opens new avenues for the development of chiroptical functional materials.

Interplay of Circularly Polarized Light with Molecular and Structural Chirality: Chiral Lanthanide Complexes and Cellulose Nanocrystals

AbstractThe interaction of circularly polarized (CP) light with chiral matter at different scales opens several possibilities of light manipulation in photonic and electronic devices. Here it is shown that in a multilayer architecture, it is possible to take advantage of the polarization‐selective reflection of the nematic arrangement of cellulose nanocrystals and the strong intrinsic CP luminescence (CPL) of the various bands of chiral Eu complexes. In this way, both the intrinsic CPL and total emission of the complex are modified depending on the enantiomer applied and on the detection geometry. This concept may apply for polarization control in electronic and photonic devices and polarized optical cavities.

Optically Ambidextrous Reflection Circularly Polarized Luminescence Film with High Dissymmetry Factor and On‐Demand Handedness

AbstractThe self‐assembled cellulose nanocrystal (CNC) film has a left‐handed layered structure, which makes the reflection of right‐handed circularly polarized (CP) light a challenge. Herein, a nematic phase layer is designed and inserted into the chiral organization, to work as a half‐wave retarder and make the ambidextrous CP light reflection. The maximum reflectivity exceeds 80%, which breaks the 50% limitations of single‐direction light reflection and is the current maximum in all the reported CNC‐based films. This “sandwich‐like” structure displays different optical properties on both sides, displayed as the chromatism and the inversion of the circular dichroism signals. The dual CP light reflection and direction‐dependent optical phenomena are reserved in the synthesized circularly polarized luminescence (CPL) film, with the dissymmetry factor (glum) of −0.4245. However, this luminescent intensity and single‐direction emission are not enough in advanced optical systems. This work designs a triple CPL amplification path and develops the handedness inversion strategy, with the glum of −1.0551 and 0.4082. Then, the dual‐directional CPL emission films are designed, where the chiral optics can be switched on‐demand. Finally, the photonic crystal films are applied in the anti‐counterfeit and chiral superstructure induction.

Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling

Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a |glum| value up to 0.11. The microcrystals were prepared from highly emissive difluoroboron β‐diketonate (BF2dbk) dyes R‐1 or S‐1 with chiral binaphthol (BINOL) skeletons. R‐1 and S‐1 exhibit undetectable CPL signals in solution but manifest intense CPL emission in their chiral microcrystals. The chiral superstructures induced by BINOL skeletons were confirmed by XRD analysis. Spectral analysis and theoretical calculations indicate that intermolecular electronic coupling, mediated by the asymmetric stacking in the chiral superstructures, effectively alters excited‐state electronic structures and facilitates electron transitions perpendicular to BF2bdk planes. The coupling increases cosθµ,m from 0.05 (monomer) to 0.86 (tetramer) and triggers intense optical activity of BF2bdk. The results demonstrate that optical activity of chromophores within assemblies can be regulated by both orientation and extent of intermolecular electronic couplings.

Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling.

Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a |glum| value up to 0.11. The microcrystals were prepared from highly emissive difluoroboron β-diketonate (BF2dbk) dyes R-1 or S-1 with chiral binaphthol (BINOL) skeletons. R-1 and S-1 exhibit undetectable CPL signals in solution but manifest intense CPL emission in their chiral microcrystals. The chiral superstructures induced by BINOL skeletons were confirmed by single-crystal XRD analysis. Spectral analysis and theoretical calculations indicate that intermolecular electronic coupling, mediated by the asymmetric stacking in the chiral superstructures, effectively alters excited-state electronic structures and facilitates electron transitions perpendicular to BF2bdk planes. The coupling increases cosθμ,m from 0.05 (monomer) to 0.86 (tetramer) and triggers intense optical activity of BF2bdk. The results demonstrate that optical activity of chromophores within assemblies can be regulated by both orientation and extent of intermolecular electronic couplings.

Unraveling the Origin of Multichannel Circularly Polarized Luminescence in a Pyrene-Functionalized Topologically Chiral [2]Catenane.

Mechanically interlocked molecules (MIMs) are promising platforms for developing functionalized artificial molecular machines. The construction of chiral MIMs with appealing circularly polarized luminescence (CPL) properties has boosted their potential application in biomedicine and the optical industry. However, there is currently little knowledge about the CPL emission mechanism or the emission dynamics of these related MIMs. Herein, we demonstrate that time-resolved circularly polarized luminescence (TRCPL) spectroscopy combined with transient absorption (TA) spectroscopy offers a feasible approach to elucidate the origins of CPL emission in pyrene-functionalized topologically chiral [2]catenane as well as in a series of pyrene-functionalized chiral molecules. For the first time, direct evidence differentiating the chiroptical signals originating from either topological (local state emission) or Euclidean chirality (excimer state emission) in these pyrene-functionalized chiral molecules has been discovered. Our work not only establishes a novel and ideal approach to study CPL mechanism, but also provides a theoretical foundation for the rational design of novel chiral materials in the future.

Unraveling the Origin of Multichannel Circularly Polarized Luminescence in a Pyrene‐Functionalized Topologically Chiral [2]Catenane

AbstractMechanically interlocked molecules (MIMs) are promising platforms for developing functionalized artificial molecular machines. The construction of chiral MIMs with appealing circularly polarized luminescence (CPL) properties has boosted their potential application in biomedicine and the optical industry. However, there is currently little knowledge about the CPL emission mechanism or the emission dynamics of these related MIMs. Herein, we demonstrate that time‐resolved circularly polarized luminescence (TRCPL) spectroscopy combined with transient absorption (TA) spectroscopy offers a feasible approach to elucidate the origins of CPL emission in pyrene‐functionalized topologically chiral [2]catenane as well as in a series of pyrene‐functionalized chiral molecules. For the first time, direct evidence differentiating the chiroptical signals originating from either topological (local state emission) or Euclidean chirality (excimer state emission) in these pyrene‐functionalized chiral molecules has been discovered. Our work not only establishes a novel and ideal approach to study CPL mechanism, but also provides a theoretical foundation for the rational design of novel chiral materials in the future.

Fluorescence-Selective Absorption and Circularly Polarized Fluorescence Energy Transfer Assist the Generation of Multicolor Circularly Polarized Luminescence in Chiral Helical Polyacetylene-Based Janus Nanofibers.

Chiroptical nanomaterials with circularly polarized luminescence (CPL) performance have aroused increasing attention. Herein, multicolor CPL-active Janus nanofibers are prepared through a simple parallel electrospinning method using chiral helical polyacetylenes as the chiral source and achiral fluorophores as the fluorescent source. Interestingly, despite a direct spatial isolation between the chiral component and the fluorescent component, blue and green CPL emissions can still be obtained due to the fluorescence-selective absorption behavior of chiral helical polyacetylenes, with a satisfactory dissymmetric factor (glum) of 2 × 10-2 and 2.5 × 10-3, respectively. Moreover, by taking advantage of the circular polarization fluorescence energy transfer process, red CPL emission is further achieved using the obtained blue and green CPL as energy donors and the achiral red fluorophore as an energy acceptor. The present work offers a facile approach to prepare multilevel-structured chiroptical materials with promising application potentials in a flexible photoelectric device.

Tunable circularly polarized luminescence behaviors caused by the structural symmetry of achiral pyrene-based emitters in chiral co-assembled systems

The regulation of circularly polarized luminescence (CPL) behavior is of great significance for practical applications. Herein, we deliberately designed three achiral pyrene derivatives (Py-1, Py-2, and Py-3) with different butoxy-phenyl substituents and the chiral binaphthyl-based inducer (R/S-B) with anchored dihedral angle to construct chiral co-assemblies, and explored their induced CPL behaviors. Interestingly, the resulting co-assemblies demonstrate tunable CPL emission behaviors caused by the structural symmetry effect of achiral pyrene-based emitters during the chiral co-assembly process. And in spin-coated films, the dissymmetry factor (gem) values were 9.1 × 10-3 for (R/S-B)1-(Py-1)10, 5.6 × 10-2 for (R/S-B)1-(Py-2)7, and 8.6 × 10-4 for (R/S-B)1-(Py-3)1, respectively. The strongest CPL emission (|gem| = 5.6 × 10-2, λem = 423 nm, QY = 34.8 %) was detected on (R/S-B)1-(Py-2)7 due to the formation of regular and ordered helical nanofibers through the strong π-π stacking interaction between the R/S-B and the achiral Py-2 emitter. The strategy presented here provides a creative approach for progressively regulating CPL emission behaviors in the chiral co-assembly process.

Reversible Photochromism for Dynamically Tuning Full‐Color Circularly Polarized Luminescence Toward Multi‐Level Anti‐Counterfeiting Application

AbstractPhotochromic circularly polarized luminescence (CPL) demonstrates broad application prospects in the field of advanced functional materials. However, the current photochromic CPL focuses predominantly on single‐band CPL adjustment, and how to achieve dynamically tunable CPL in multi‐band is still highly challenging. This work reports the success in utilizing reversible photochromism for realizing full‐color CPL emission. Photochromic flexible films are created consisting of triple components: spiropyran (SP) working as photochromic matter, polyurethane (PU) as matrix, and chiral helical polyacetylene as chiral component. Further introducing blue fluorophore 9‐anthracene carboxylic acid (ACA) in the film, blue CPL and red CPL are emitted respectively through selective absorption/transmission and circularly polarized fluorescence energy transfer (CPF‐ET). Doping the photochromic film with diverse fluorophores provides full‐color CPL emission. Adding Zn2+ further intensifies fluorescence and CPL via forming merocyanine (MC)‐Zn2+ complex. Taking advantage of the diverse fluorescence and CPL emission, anti‐counterfeiting, and secondary encryption application of the resulting photochromic CPL materials are demonstrated.

Cholesterol-decorated porphyrin with circularly polarized luminescence: Design, synthesis and properties

Porphyrin was an excellent near-infrared dye but its rigid planar structure is not favorable for producing circularly polarized luminescence (CPL) property. Chirality transfer is an effective strategy to realize the CPL emission for achiral fluorescent unit. In this study, porphyrin derivatives with four cholesterol groups and dodecyl groups B4C and B4D were designed and synthesized. B4C and B4D exhibited good near-infrared emission in both solution and aggregated states. The solid film of B4C emitted strong left CPL fluorescence, while this CPL signal in mesomorphic film was stronger and switched to right CPL emission. The fluorescence dissymmetry factor (glum) of B4C was as high as 2.31×10−2. These results suggested the effective chirality transfer from cholesterol units to porphyrin units based on spiral columnar liquid crystalline stacking and the CPL signal of B4C was tunable by temperature, supplying a good way on design and synthesis of CPL material with tunable CPL signal based on achiral dyes.

Processable circularly polarized luminescence material enables flexible stereoscopic 3D imaging.

Endowing three-dimensional (3D) displays with flexibility drives innovation in the next-generation wearable and smart electronic technology. Printing circularly polarized luminescence (CPL) materials on stretchable panels gives the chance to build desired flexible stereoscopic displays: CPL provides unusual optical rotation characteristics to achieve the considerable contrast ratio and wide viewing angle. However, the lack of printable, intense circularly polarized optical materials suitable for flexible processing hinders the implementation of flexible 3D devices. Here, we report a controllable and macroscopic production of printable CPL-active photonic paints using a designed confining helical co-assembly strategy, achieving a maximum luminescence dissymmetry factor (glum) value of 1.6. We print customized graphics and meter-long luminous coatings with these paints on a range of substates such as polypropylene, cotton fabric, and polyester fabric. We then demonstrate a flexible textile 3D display panel with two printed sets of pixel arrays based on the orthogonal CPL emission, which lays an efficient framework for future intelligent displays and clothing.

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 (SF) 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 (SF =0.30) emitted a strong CPL signal (|glum| = 0.47). In contrast, the T-shaped derivative (PHEBen) dye (SF =0.09) showed a weak circular polarization level (|glum| = 0.07) at similar CLC textures. Most interestingly, this kind of dichroic PHECN dye with a higher SF could greatly improve the contrast ratio of CPL (Δglum = 0.47) and emission intensity (ΔFL = 46.0%) at direct-current electric field compared with the T-shaped PHEBen (Δglum = 0.07 and ΔFL = 1.0%) in CLCs. 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.

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

AbstractIt 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 (SF) 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 (SF=0.30) emitted a strong CPL signal (|glum|=0.47). In contrast, the T‐shaped derivative (PHEBen) dye (SF=0.09) showed a weak circular polarization level (|glum|=0.07) at similar CLC textures. Most interestingly, this kind of dichroic PHECN dye with a higher SF could greatly improve the contrast ratio of CPL (Δglum=0.47) and emission intensity (ΔFL=46.0 %) at direct‐current electric field compared with the T‐shaped PHEBen (Δglum=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.

Asymmetric Synthesis of Tetraphenylethylene Helicates and Their Full-Color CPL Emission with High glum and High Fluorescence Quantum Yield.

Tetraphenylethylene (TPE) helicates with single helical handedness not only owe high fluorescence quantum yield but also possess good helical chirality, showing an excellent circularly polarized luminescence active material. In this work, a new method for directly obtaining single-handed TPE helicates has been developed. By using chiral p-phenylenediamine derivatives as an intramolecular cyclization reagent of TPE, the single-handed propeller-like conformation and stable helical chirality of the TPE unit were obtained, avoiding complicated and expensive HPLC chiral column separation. The as-prepared chiral TPE helicates displayed strong emission with an almost quantitative fluorescence quantum yield (Φf) and strong circularly polarized luminescence (CPL). In addition, the chirality and CPL signals of the TPE helicates could be significantly magnified by the helical arrangement together with 4'-pentyl-4-biphenylcarbonitrile (5CB) liquid crystal molecules. Moreover, full-color CPL emissions with both a high absolute CPL dissymmetrical factor up to 0.43 and high Φf were afforded.

Circularly polarized luminescence switch based on a photochromic europium(III) helicate derived coordination polymer

Chiroptical switches based on circularly polarized luminescence (CPL) have shown the promising applications in advanced information technologies. Herein, a pair of lanthanide coordination polymer enantiomers [Eu2(LR)3(BTFPO)2]n and [Eu2(LS)3(BTFPO)2]n with light-regulated CPL property are designed, which are assembled by a chiral binuclear triple-stranded Eu3+ helicates [Eu2(LR/S)3] coordinated with two photochromic triphenylphosphine oxides (BTFPO). Upon the alternative UV and 526 nm light irradiation, the complexes show the reversible photochromism, PL and CPL responses. Notably, the luminescence dissymmetry factor, glum of 5D0→7F1 (591 nm) transition shows an obvious increase from 0.19 to 0.29 before and after 275 nm light irradiation. Additionally, the emission from Eu3+ center is not completely quenched in closed-ring state due to the low photocyclization (Фo-c) quantum yield of the polymer. The partial maintenance of emissive intensity is of essential importance for the monitor of CPL signal. More importantly, the CPL photo-switching property of the complexes in solid hybrid film is maintained, and still displays the enhanced CPL emission in photostationary state. Further, the potential applications of the doping film in logic gate and anti-counterfeiting were investigated.

Redox‐Modulated Circularly Polarized Luminescence in Chiral Photonic Films Derived from Cellulose Nanocrystals and Polyoxometalate

AbstractAchieving smart circularly polarized luminescence (CPL) materials with large luminescence dissymmetry factor (glum) is in high demand for potential technological applications in the chiroptical fields. Herein, a series of chiral photonic crystals (CPCs) derived from cellulose nanocrystals (CNCs) and photosensitive inorganic polyoxometalates (POMs) through an evaporation‐induced self‐assembly strategy are reported. The photonic bandgaps (PBGs) of CPC films are well regulated by controlling the amount of doped POMs, yielding the tunable right‐handed CPL emission with tailored glum. By locating the maximum emission peak of POMs at the center of the PBG of CPC films, the composite shows remarkable CPL performance with a |glum| value up to 0.53. Furthermore, the CPL can be reversibly switched on/off through a fluorescence resonance energy transfer (FRET) process controlled by alternate UV irradiation reduction and air oxidation. The CPC films hold the great promise as next‐generation chiroptical memory devices.

Helical Polymer Working as a Chirality Amplifier to Generate and Modulate Multicolor Circularly Polarized Luminescence in Small Molecular Fluorophore/Polymer Composite Films.

In-depth studies of chirality and circularly polarized luminescence (CPL) have become indispensable in the process of learning human nature. Small molecules with CPL activity are one of the research hotspots. However, the CPL properties of such materials are generally not satisfying. Here, we synthesized a series of chiral small molecular fluorophores that cannot demonstrate CPL emission themselves. By introducing an optically inactive helical polymer, chirality transfer and chirality amplification efficiently occur, thereby generating intense CPL emission. Through combining different chiralized fluorophores, multicolor CPL-active films with emission wavelength centered at 463, 525, and 556 nm were fabricated, with the maximum luminescence dissymmetry factor (glum) being up to -0.028. Then, benefiting from the strong CPL emission and appropriate energy donor-acceptor system, we further established a circularly polarized fluorescence-energy transfer (CPF-ET) strategy in which the CPL-active films work as a donor emitting circularly polarized fluorescence to excite an achiral fluorophore (Nile red) as the acceptor, producing red CPL with glum of up to -0.011 at around 605 nm.

Stepwise Solution-Interfacial Nanoarchitectonics for Assembled Film with Full-Color and White-Light Circularly Polarized Luminescence.

The fabrication of chiral thin films with tunable circularly polarized luminescence (CPL) colors is important in developing chiroptical materials but remains challenging due to the lack of assembly-initiated chiral film formation methodology. Here, by adopting a combined solution aggregation and interfacial assembly strategy, we report the fabrication of chiral film materials with full-color and white-light CPL. A biquinoline glutamic acid ester (abbreviated as BQGE) shows a typical aggregation-induced emission property with blue CPL after solution aggregation. Subsequent interfacial assembly of these solution aggregates on a solid substrate leads to the formation of a CPL active film consisting of nanobelt structures. Since the BQGE molecule has a coordination site, the CPL emission of an individual BQGE film can be extended from blue to green emission upon coordination with a zinc ion, accompanied by morphology transition from nanobelts to nanofibers. Further extension to red-color CPL is successfully achieved by coassembly with an achiral acceptor dye. Interestingly, the proper combination of coordination ratio and acceptor loading ratio provides bright white-light CPL emission from the BQGE/Zn2+/PDA triad composite film. This work provides a new approach to fabricating chiroptical film materials with controlled microscopic morphology and tunable CPL properties.