Circularly Polarized Luminescence Signals Research Articles

Chiral Co‐assembly Based on a Stimuli‐Responsive Polymer towards Amplified Full‐Color Circularly Polarized Luminescence

AbstractStimuli‐responsive circularly polarized luminescence (CPL) materials have been attaching wide attention in the field of optical information storage and encryption, while still facing the challenge of the realization of high luminescence dissymmetry factors (glum). This work presents a pair of stimuli‐responsive chiral co‐assemblies P7R3 and P7S3 by combining polymer PFIQ containing iso‐quinoline units with chiral inducers. The obtained chiral co‐assemblies can reversibly undergo significant modification in CPL behavior under trifluoroacetic acid (TFA) fumigation and annealing treatment, with the |glum| values exhibiting a reversible shift between 0.2 and 0.3. Moreover, the chiral co‐assemblies before TFA fumigating can effectively induce achiral emitters to generate intense full‐color CPL signals through CPL energy transfer (CPL‐ET), with the corresponding |glum| values larger than 0.2. Moreover, information encryption and decryption as well as a multi‐level logic gates application are achieved by leveraging the reversible stimuli‐responsive CPL activity of the chiral co‐assembly. This work provides a new perspective for the construction of stimuli‐responsive chiral luminescent materials with large |glum| values and the activation of CPL behavior in achiral emitters.

Sign Inversion of Circularly Polarized Luminescence in Cholesteric Liquid Crystals Induced by Mercury Ions through Binaphthyl Dopants′ Conjugation Control

AbstractStimuli‐responsive circularly polarized luminescence (CPL) materials based on cholesteric liquid crystal (CLC) platforms show great promise for applications in information encryption and anticounterfeiting. In this study, we constructed a mercury ion‐responsive CPL system in CLCs by controlling the conjugation degree of axially chiral binaphthyl derivatives. Two chiral binaphthyl derivatives (R/S‐1 and R/S‐2) were initially used as chiral dopants to demonstrate that CPL inversion (glum values from 0.5/‐0.44 to −0.53/0.48) in CLCs could be achieved by modulating the conjugation degree of the chiral binaphthyls. Based on this concept, the thioacetal binaphthyl R‐2S was developed and used as a mercury‐responsive chiral dopant in CLCs. Under Hg ion treatment, the CPL sign inverted (glum value changed from 0.22 to −0.29) due to the transformation of the thioacetal into an aldehyde group. Additionally, the mercury ion‐responsive CPL material was applied in information encryption.

Chiral Co-assembly Based on a Stimuli-Responsive Polymer towards Amplified Full-Color Circularly Polarized Luminescence.

Stimuli-responsive circularly polarized luminescence (CPL) materials have been attaching wide attention in the field of optical information storage and encryption, while still facing the challenge of the realization of highluminescence dissymmetryfactors (glum). This work presents a pair of stimuli-responsive chiral co-assemblies P7R3 and P7S3 by combining polymer PFIQ containing iso-quinoline units with chiral inducers. The obtained chiral co-assemblies can reversibly undergo significant modification in CPL behavior under trifluoroacetic acid (TFA) fumigation and annealing treatment, with the |glum| values exhibiting a reversible shift between 0.2 and 0.3. Moreover, the chiral co-assemblies before TFA fumigating can effectively induce achiral emitters to generate intense full-color CPL signals through CPL energy transfer (CPL-ET), with the corresponding |glum| values larger than 0.2. Moreover, information encryption and decryption as well as a multi-level logic gates application are achieved by leveraging the reversible stimuli-responsive CPL activity of the chiral co-assembly. This work provides a new perspective for the construction of stimuli-responsive chiral luminescent materials with large |glum| values and the activation of CPL behavior in achiral emitters.

Sign Inversion of Circularly Polarized Luminescence in Cholesteric Liquid Crystals Induced by Mercury Ions through Binaphthyl Dopants' Conjugation Control.

Stimuli-responsive circularly polarized luminescence (CPL) materials based on cholesteric liquid crystal (CLC) platforms show great promise for applications in information encryption and anticounterfeiting. In this study, we constructed a mercury ion-responsive CPL system in CLCs by controlling the conjugation degree of axially chiral binaphthyl derivatives. Two chiral binaphthyl derivatives (R/S-1 and R/S-2) were initially used as chiral dopants to demonstrate that CPL inversion (glum values from 0.5/-0.44 to -0.53/0.48) in CLCs could be achieved by modulating the conjugation degree of the chiral binaphthyls. Based on this concept, the thioacetal binaphthyl R-2S was developed and used as a mercury-responsive chiral dopant in CLCs. Under Hg ion treatment, the CPL sign inverted (glum value changed from 0.22 to -0.29) due to the transformation of the thioacetal into an aldehyde group. Additionally, the mercury ion-responsive CPL material was applied in information encryption.

Novel AIE liquid crystals with high CPL-active bearing multiple dodecyl/cholesterol-decorated R-BINOL-cyanostilbene

The well-structured circularly polarized luminescence (CPL) active liquid crystal materials (R-BINC-Al and R-BINC-Ch) were synthesized through Suzuki coupling of the R-binaphthyl-cyanostilbene unit, followed by modification with dodecyl chains or cholesterol groups. The influence of chiral sources on the liquid crystal behavior, optical properties, and chiroptical response of R-BINC-Al and R-BINC-Ch was thoroughly investigated. Such results revealed that both molecules exhibited typical aggregation-induced emission (AIE) properties and strong solid-state fluorescence. Concretely, the quantum efficiency (ΦF) values of samples with multiple chiral sources increased from 46 % to 51 % by forming liquid crystals in the smectic C and cholesteric phases, the chirality can be transferred to the cyanostilbene unit through ordered self-assembly in the mesophase, resulting in a significant CPL signal across the molecules. Rightfully, the dissymmetry factor (glum) was increased from -7.92 × 10–3 to -1.53 × 10–2 with the introduction of chiral cholesteryl groups. our work elucidated the relationship between multiple chiral sources and CPL behavior, offering a systematic approach to designing chiral luminescent materials in the liquid-crystal phase with high ΦF and substantial glum values, providing a theoretical framework for potential applications in optoelectronic devices.

Synthesis and properties of chiral liquid crystal copolymers with tunable circularly polarized luminescence

Chiral liquid crystals have received widespread attention due to their unique advantages in improving circularly polarized luminescence (CPL) properties. However, how to achieve the emission and modulation of CPL for chiral liquid crystals within intrinsic polymer-based materials through a simple strategy remains a challenge. This article proposes a simple and feasible method to synthesize CPL chiral liquid crystals and manipulate their properties by copolymerizing chiral liquid crystal monomer with luminescent monomer. A series of intrinsic chiral luminescent liquid crystal copolymers C*(x)-Py(y) with tunable CPL performance were synthesized by copolymerizing chiral liquid crystal monomer MA6C* with pyrene-based luminescent monomer MC6Py in varying ratios. The effective control of the chiral liquid crystal phase structure and CPL performance of the copolymers C*(x)-Py(y) can be achieved by altering the composition of copolymers. In the copolymers, the CPL signal is generated due to the helix induction of pyrene chromophores by the chiral liquid crystals, and the CPL signal can be inverted and amplified by the unique selective reflection properties of chiral liquid crystals. For copolymer C*(0.75)-Py(0.25), the luminescence dissymmetry factor value and solid-state fluorescence quantum yield can reach −0.052 and 43.12%, respectively.

Multifaceted regulation of chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers

AbstractThe multifaceted regulation of the chiroptical properties and self‐assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve. Herein, a series of novel salen‐based chiral fluorescent polymers with aggregation‐induced emission and varied substitution manners were facilely and efficiently synthesized. Multiple factors were systematically investigated on the chiroptical properties and self‐assembly performance of these polymers, which include molecular structures, solvent environments, metal coordination, and liquid crystal (LC) assemblies. Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers, from single‐handed helical fibers, helical toroids or loops, to spherical structures, consequently leading to an aggregation‐reduced circular dichroism (CD) phenomenon. The polymers bearing salen units show highly selective and reversible coordination with Zn2+ and can also induce multiple responses in the absorption, luminescence, CD, and circularly polarized luminescence (CPL) of these chiral fluorescent polymers via a coordination‐ and dissociation‐initiated self‐assembly tuning. Furthermore, a small amount of the chiral fluorescent polymer in can induce achiral nematic 4‐cyano‐4′‐n‐pentylbiphenyl (5CB) to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal. The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10−1.

A Halogen‐Bonded Fluorescent Molecular Photoswitch: Transition from 3D Cubic Lattice to 1D Helical Superstructure for Polarization Inversion of Circularly Polarized Luminescence

AbstractThe fabrication of materials that can switch between circularly polarized luminescence (CPL) signals is both essential and challenging. Here, two new halogen‐bonded fluorescent molecular photoswitches, namely, HB‐switch 1 and HB‐switch 2, containing α‐cyano‐substituted diarylethene compounds with different end groups were developed. Upon exposure to specific UV or visible light wavelengths, they exhibited controllable and reversible Z/E photoisomerization. When these switches were integrated into blue‐phase liquid crystals (BPLCs), the temperature range of BP significantly expanded. Notably, the BP system incorporating HB‐switch 1 exclusively achieved reversible polarization inversion of CPL signals under irradiation with specific UV/Visible light and during cooling/heating. The photo/thermal dual‐response behavior of the CPL signals can be attributed to the phase transition from a high‐symmetry 3D BP Icubic lattice to a low‐symmetry 1D helical superstructure induced by the Z/E photoisomerization of HB‐switch 1 and temperature changes. This study underscores the significance of employing halogen‐bond assembly strategies to design materials with switchable CPL signals, opening new possibilities for CPL‐active systems.

A Halogen-Bonded Fluorescent Molecular Photoswitch: Transition from 3D Cubic Lattice to 1D Helical Superstructure for Polarization Inversion of Circularly Polarized Luminescence.

The fabrication of materials that can switch between circularly polarized luminescence (CPL) signals is both essential and challenging. Here, two new halogen-bonded fluorescent molecular photoswitches, namely, HB-switch 1 and HB-switch 2, containing α-cyano-substituted diarylethene compounds with different end groups were developed. Upon exposure to specific UV or visible light wavelengths, they exhibited controllable and reversible Z/E photoisomerization. When these switches were integrated into blue-phase liquid crystals (BPLCs), the temperature range of BP significantly expanded. Notably, the BP system incorporating HB-switch 1 exclusively achieved reversible polarization inversion of CPL signals under irradiation with specific UV/Visible light and during cooling/heating. The photo/thermal dual-response behavior of the CPL signals can be attributed to the phase transition from a high-symmetry 3D BP Icubic lattice to a low-symmetry 1D helical superstructure induced by the Z/E photoisomerization of HB-switch 1 and temperature changes. This study underscores the significance of employing halogen-bond assembly strategies to design materials with switchable CPL signals, opening new possibilities for CPL-active systems.

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.

Dynamic Near‐Infrared Circularly Polarized Luminescence Encoded by Transient Supramolecular Chiral Assemblies

AbstractCircularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near‐infrared (NIR) CPL‐active materials, especially those that exhibit high glum values and can be controlled spatially and temporally, are rare. Herein, dynamic NIR‐CPL with a glum value of 2.5×10−2 was achieved through supramolecular coassembly and energy‐transfer strategies. The chiral assemblies formed by the coassembly between adenosine triphosphate (ATP) and a pyrene derivative exhibited a red CPL signal (glum of 10−3). The further introduction of sulfo‐cyanine5 resulted in a energy‐transfer process, which not only led to the NIR CPL but also increased the glum value to 10−2. Temporal control of these chiral assemblies was realized by introducing alkaline phosphatase to fabricate a biomimetic enzyme‐catalyzed network, allowing the dynamic NIR CPL signal to be turned on. Based on these enzyme‐regulated temporally controllable dynamic CPL‐active chiral assemblies, a multilevel information encryption system was further developed. This study provides a pioneering example for the construction of dynamic NIR CPL materials with the ability to perform temporal control via the supramolecular assembly strategy, which is expected to aid in the design of supramolecular complex systems that more closely resemble natural biological systems.

Dynamic Near-Infrared Circularly Polarized Luminescence Encoded by Transient Supramolecular Chiral Assemblies.

Circularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near-infrared (NIR) CPL-active materials, especially those that exhibit high glum values and can be controlled spatially and temporally, are rare. Herein, dynamic NIR-CPL with a glum value of 2.5×10-2 was achieved through supramolecular coassembly and energy-transfer strategies. The chiral assemblies formed by the coassembly between adenosine triphosphate (ATP) and a pyrene derivative exhibited a red CPL signal (glum of 10-3). The further introduction of sulfo-cyanine5 resulted in a energy-transfer process, which not only led to the NIR CPL but also increased the glum value to 10-2. Temporal control of these chiral assemblies was realized by introducing alkaline phosphatase to fabricate a biomimetic enzyme-catalyzed network, allowing the dynamic NIR CPL signal to be turned on. Based on these enzyme-regulated temporally controllable dynamic CPL-active chiral assemblies, a multilevel information encryption system was further developed. This study provides a pioneering example for the construction of dynamic NIR CPL materials with the ability to perform temporal control via the supramolecular assembly strategy, which is expected to aid in the design of supramolecular complex systems that more closely resemble natural biological systems.

When quantum dots meet blue phase liquid crystal elastomers: visualized full-color and mechanically-switchable circularly polarized luminescence

Polymer-based circularly polarized luminescence (CPL) materials with the advantage of diversified structure, easy fabrication, high thermal stability, and tunable properties have garnered considerable attention. However, adequate and precise tuning over CPL in polymer-based materials remains challenging due to the difficulty in regulating chiral structures. Herein, visualized full-color CPL is achieved by doping red, green, and blue quantum dots (QDs) into reconfigurable blue phase liquid crystal elastomers (BPLCEs). In contrast to the CPL signal observed in cholesteric liquid crystal elastomers (CLCEs), the chiral 3D cubic superstructure of BPLCEs induces an opposite CPL signal. Notably, this effect is entirely independent of photonic bandgaps (PBGs) and results in a high glum value, even without matching between PBGs and the emission bands of QDs. Meanwhile, the lattice structure of the BPLCEs can be reversibly switched via mechanical stretching force, inducing on-off switching of the CPL signals, and these variations can be further fixed using dynamic disulfide bonds in the BPLCEs. Moreover, the smart polymer-based CPL systems using the BPLCEs for anti-counterfeiting and information encryption have been demonstrated, suggesting the great potential of the BPLCEs-based CPL active materials.

The Mn2+‐Doped Chiral 2D Perovskite with Strong Orange Fluorescent and Enhanced Circularly Polarized Luminescence

AbstractRecently, the potential circularly polarized luminescence (CPL) property of chiral 2D organic–inorganic hybrid perovskites has garnered attention due to their strong stability. However, the photoluminescence (PL) intensity of chiral 2D perovskite is generally low, which undoubtedly limits its development. Therefore, improving the PL and CPL intensity of chiral 2D perovskite has become an important focal point. To overcome this problem, a series of Mn2+‐doped R/S‐(MPEA)2PbBr4 thin films is successfully synthesized. The Mn2+‐doped films can produce strong orange emission under UV excitation with the highest photoluminescence quantum yield (PLQY) of 37.37%, a high value among reported chiral 2D perovskites. Moreover, all Mn: (R/S‐MPEA)2PbBr4 films show symmetric CPL signals. The flexible regulation of CPL is meaningful for applications, which is generally lacking in current studies. Here, it is found that the strength of CPL can be effectively regulated by doping guanidine (Gua), and the maximum glum value of 1.4 × 10−2 and PLQY of 51.31% is achieved, which are the highest among reported chiral 2D perovskites. This work provides a new idea for the development of CPL‐active materials and lays the foundation for spin devices based on chiral hybrid 2D perovskite.

Water-Regulated Evolution of Inversion, Reinversion, and Amplification of Circularly Polarized Luminescence of Supramolecular Organogels Based on Glutamide-Cyanostilbene Amphiphile.

Water incorporated with supramolecular building blocks in organic solvents can play a key role in the circularly polarized luminescence (CPL) inversion and amplification of supramolecular assemblies. Herein, we demonstrate that fine-tuning the water content regulated the assembly structure evolution and made the circular dichroism and CPL sign of the system undergo intriguing inversion, reinversion, and amplification processes based on a unique and interesting glutamide-cyanostilbene system, as supported by morphology, spectroscopic observations, and time-dependent density functional theory calculation.

Mechano-responsive chiral gold(I) complexes with aggregation- and crystallization-induced circularly polarized luminescence

Chiral materials with circularly polarized luminescence (CPL) have attracted extensive attention due to their unique optical properties. However, it is still a challenge to obtain efficient CPL materials. In this work, noticeable CPL signals were obtained through simple crystallization in the classical aggregation-caused quenching (ACQ)-typed chloro-gold(I) complexes (R)-BINAP-AuCl and (S)-BINAP-AuCl. They exhibited typical crystallization-induced emission (CIE) and crystallization-induced CPL behaviors. Importantly, after rational modification by introducing carbazole units, the resulting carbazole-gold(I) complexes (R)-BINAP-AuCz and (S)-BINAP-AuCz showed remarkable aggregation-induced phosphorescent emission (AIPE) and unique aggregation-induced CPL characteristics due to the formation of highly ordered helical packing modes in the nano-aggregate state. More interestingly, the solids of chiral carbazole-gold(I) complexes (R)-BINAP-AuCz and (S)-BINAP-AuCz could sensitively respond to external stimuli and exhibited mechano-responsive CPL performance, which was tuned by the intermolecular C–H···π interactions. Thus, this work provided a new way for constructing high-performance and smart CPL materials.

Manipulating Chiroptical Activities in 0D Chiral Hybrid Manganese Bromides by Solvent Molecular Engineering.

0D hybrid metal halides (0D HMHs) with fully isolated inorganic units provide an ideal platform for studying the correlations between chiroptical activities and crystal structures at atomic levels. Here, through the incorporation of different solvent molecules, a series of 0D chiral manganese bromides (RR/SS-C20H28N2)3MnBr8·2X (X = C2H5OH, CH3OH, or H2O) are synthesized to elucidate their chiroptical properties. They show negligible circular dichroism signals of Mn absorptions due to C2v-symmetric [MnBr4]2- tetrahedra. However, they display distinct circularly polarized luminescence (CPL) signals with continuously increased luminescence asymmetry factors (glum) from 10-4 (X = C2H5OH) to 10-3 (X = H2O). The increased glum value is structurally revealed to originate from the enhancement of [MnBr4]2- tetrahedral bond-angle distortions, due to the presence of different solvent molecules. Furthermore, (RR/SS-C20H28N2)MnBr4·H2O enantiomers with larger bond-angle distortions of [MnBr4]2- tetrahedra are synthesized based on hydrobromic acid-induced structural transformation of (RR/SS-C20H28N2)3MnBr8·2H2O enantiomers. Therefore, such (RR/SS-C20H28N2)MnBr4·H2O enantiomers exhibit enhanced CPL signals with |glum| up to 1.23×10-2. This work provides unique insight into enhancing chiroptical activities in 0D HMH systems.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Amplified Circularly Polarized Luminescence Behavior in Chiral Co-assembled Liquid Crystal Polymer Films via the Strategic Manipulation of Chiral Inducers.

One of the most important factors for the future application of circularly polarized luminescence (CPL) materials is their high dissymmetry factors (gem), and more and more studies are working tirelessly to focus on increasing the gem value. Herein, we chose an achiral liquid crystal polymer (LC-P) and two chiral binaphthyl-based inducers (R/S-3 and R/S-6) with different substitution positions (3,3' positions for R/S-3 and 6,6' positions for R/S-6) to construct chiral co-assemblies and explored their induced amplification CPL behaviors. Interestingly, after the thermal annealing treatment, this kind of chiral co-assembly (R/S-3)0.05-(LC-P)0.95 can emit a superior CPL signal (|gem| = 0.31 and λem = 424 nm), which achieves about 13-fold signal amplification in the spin-coated film, compared to (R/S-6)0.1-(LC-P)0.9 (|gem| = 0.023 and λem = 424 nm). This is because (R/S-3)0.05-(LC-P)0.95 could further co-assemble to form a more ordered arrangement LC state and generate regular helix nanofibers than that of (R/S-6)0.1-(LC-P)0.9. This work provides an efficient method for synthesizing high-quality CPL-active materials through the strategic manipulation of the structure of chiral binaphthyl-based inducers in chiral co-assembled LCP systems.