Polarized Luminescence Research Articles

Sequence Engineering in Tuning the Circularly Polarized Luminescence of Aggregation-Induced Emission-Active Hetero[3]rotaxanes

Sequence Engineering in Tuning the Circularly Polarized Luminescence of Aggregation-Induced Emission-Active Hetero[3]rotaxanes

Flexible Organic Crystal with Two-Dimensional Elastic Bending and Recoverable Plastic Twisting for Circularly Polarized Luminescence

Flexible Organic Crystal with Two-Dimensional Elastic Bending and Recoverable Plastic Twisting for Circularly Polarized Luminescence

Color-Tunable Perovskite Nanomaterials with Intense Circularly Polarized Luminescence and Tailorable Compositions.

The ability to design halide perovskite nanocrystals (PNCs) with circularly polarized luminescence (CPL) offers exceptional potential in photonic technologies. Despite recent inspiring advances, the creation of PNCs with full-color tailorablity, outstanding CPL, and long-term stability remains a substantial challenge. Herein, a robust strategy to craft CPL-active PNCs is reported, exhibiting appealing full-color tunable wavelengths, enhanced CPL, and prolonged stability. In contrast to conventional methodologies, this strategy utilizes chiral nematic mesoporous silica (CNMS) as host to render in situ confined growth of diverse achiral PNCs. By strategically engineering photonic bandgap, adjusting loading amount of PNCs, and manipulating cations/anion compositions of PNCs, robust CPL responses with tunable wavelength and intensity are successfully obtained. The resulting PNCs-CNMS achieves stable CPL emissions with full-color tunability and impressive luminescent dissymmetric factors up to -0.17. Remarkably, silica-based hosts as a protective barrier confer exceptional resistance to humidity, photodegradation, and thermal stability, even up to 95 °C. Furthermore, the ability to achieve reversible CPL switching within PNCs-CNMS is attainable by leveraging the responsiveness of CNMS matrix or dynamic behavior of impregnated PNCs. Additionally, circularly polarized light-emitting diode devices based on PNCs-CNMS can be conveniently fabricated. This research affords a powerful platform for designing functional chiroptical materials.

Strong Circularly Polarized Luminescence Promoted by AIE-active Chiral Co-assemblies in Liquid Crystal Polymer Films.

Recently, extensive works have focused on increasing the dissymmetry factors (glum) of various circularly polarized luminescence (CPL) materials, which is one of the most important factors for future applications of CPL. Herein, we designed a chiral co-assembled liquid crystal polymer (LCP) PTZ@R/S-PB2, which was prepared by chiral binary co-polymer (R/S-PB2) doped with achiral phenothiazine derivation dye (PTZ). For comparison, ternary co-polymerized LCP (R/S-PT) was synthesized by co-polymerizing with mesogenic monomer, chiral monomer and emissive monomer. Both PTZ@R/S-PB2 and R/S-PT showed aggregation-induced emission (AIE) properties. Interestingly, the CPL signals of both PTZ@R/S-PB2 and R/S-PT were reversed and amplified after thermal annealing treatment. The |glum| values of the co-assembled PTZ@R/S-PB2 were up to 0.13 at a 32 nm thickness, which was 5.4 times that of R/S-PT (|glum|=0.024). This is due to PTZ@R/S-PB2 could form more orderly chiral co-assembly structures. Noticeably, increasing the LCP film thickness could further improve the glum value, and the maximum glum of PTZ@R/S-PB2 could be enhanced to +0.91/-0.82 at a 220 nm thickness.

Dual Stimuli-Responsive [2]Rotaxanes with Tunable Vibration-Induced Emission and Switchable Circularly Polarized Luminescence.

Aiming at the construction of novel stimuli-responsive fluorescent system with precisely tunable emissions, the typical 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration-induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli-responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC-functionalized [2]rotaxanes display interesting VIE behaviors including white-light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion-induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors (glum ) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5-fold increase in glum values up to -0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use.

Dual Stimuli‐Responsive [2]Rotaxanes with Tunable Vibration‐Induced Emission and Switchable Circularly Polarized Luminescence

AbstractAiming at the construction of novel stimuli‐responsive fluorescent system with precisely tunable emissions, the typical 9,14‐diphenyl‐9,14‐dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration‐induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli‐responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC‐functionalized [2]rotaxanes display interesting VIE behaviors including white‐light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion‐induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors (glum) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5‐fold increase in glum values up to −0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use.

A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence.

Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized chiral framework is conducive to directing π-π self-assembly and delivering a strong and persistent CPL signal. Here, perylene diimides (PDIs) are an excellent choice for the organic dye component because, alongside their tunable photophysical and self-assembly properties, functionalization of the PDI's core yields a twisted, chiral π-system, capable of CPL. However, configurationally stable PDI-based macrocycles are rare, and those that are also capable of π-π self-assembly beyond dimers are unprecedented, both of which are advantageous for robust self-assembled chiroptical materials. In this work, we report the first bay-connected bis-PDI macrocycle that is configurationally stable (ΔG⧧ > 155 kJ mol-1). We use this chirally locked macrocycle to uncover new knowledge of chiral PDI self-assembly and to perform new quantitative CPL imaging of the resulting single-crystal materials. As such, we discover that the chirality of a 1,7-disubstituted PDI provides a rational route to designing H-, J- and concomitant H- and J-type self-assembled materials, important arrangements for optimizing (chir)optical and charge/energy transport properties. Indeed, we reveal that CPL is amplified in the single crystals of our chiral macrocycle by quantifying the degree of emitted light circular polarization from such materials for the first time using CPL-Laser Scanning Confocal Microscopy.

Induced Absolute Configuration of Achiral Tetradentate Ligands in Metal–Organic Frameworks for Circularly Polarized Luminescence

Comprehensive SummaryThe crystallization of chiral molecules is of great significance to understand the origin and evolution of hierarchical chirality and reveal the relationships between structural chirality and circularly polarized luminescence (CPL) activity. Here, we report two pairs of chiral metal–organic frameworks (MOFs) (DCF‐17/LCF‐17, DCF‐18/LCF‐18) by utilizing tetradentate ligands tetra(3‐imidazoylphenyl)ethylene (TIPE) and 4,4'‐[4',5'‐bis[4‐(4‐pyridinyl)phenyl][1,1':2',1”‐terphenyl]‐4,4”‐diyl]bis[pyridine] (TPPP) as linkers. It can be observed that the spontaneous resolution of the achiral ligands is converted into the induced resolution, and the ligands form the absolute configuration by using enantiopure camphoric acid (cam) as chiral induced reagent (CIR). As a result, the racemate MOFs can be driven to generate absolute homochiral crystallization. Another two achiral MOFs [Cd(D‐cam)(TPPP)0.5] (AF‐1, AF = achiral framework) and [Cd(L‐cam)(TPPP)0.5] (AF‐2) were prepared. The position disorder of D/L‐cam skeleton causes the generation of nonchiralization, further leading to disappearance of symmetry breaking of TPPP. For the perspective of structure, this is the first report which reveals the chiral transfer and nonchiralization between chiral induced agents and tetradentate ligands. Besides, DCF‐17 and LCF‐17 show CPL with luminescence dissymmetry factor (glum) of –1.0 × 10‐2 and +9.2 × 10–3, respectively. This work provides the useful evidences to reveal the induced chiral crystallization and the construction of CPL‐active crystalline materials.

Induced Circularly Polarized Luminescence and Exciton Fine Structure Splitting in Magnetic-Doped Chiral Perovskites.

Magnetic impurity doping in semiconductors has emerged as an important strategy to endow exotic photophysical and magnetic properties. While most reported hosts are centrosymmetric semiconductors, doping magnetic ions into a noncentrosymmetric chiral semiconductor can offer additional control of photonic and spin polarization. In this work, we synthesized a Mn2+-doped chiral two-dimensional (2D) perovskite, Mn2+:(R-MPA)2PbBr4 (R-MPA+ = R-methyl phenethylammonium). We found that the optical activity of chiral 2D perovskites is enhanced with an increased concentration of Mn2+ ions. Additionally, efficient energy transfer from the chiral host to the Mn2+ dopants is observed. This energy transfer process gives rise to circularly polarized luminescence from the excited state of Mn2+ (4T1 → 6A1), exhibiting a photoluminescence quantum yield up to 24% and a dissymmetry factor of 11%. The exciton fine structures of undoped and Mn2+-doped (R-MPA)2PbBr4 are further studied through magnetic circular dichroism (MCD) spectroscopy. Our analysis shows that chiral organic cations lead to an exciton fine structure splitting energy as large as 5.0 meV, and the splitting is further increased upon Mn2+ doping. Our results reveal the strong impacts of molecular chirality and magnetic dopants on the exciton structures of halide perovskites.

One-Pot Synthesis, Circularly Polarized Luminescence, and Controlled Self-Assembly of Janus-Type Miktoarm Star Copolymers.

With the aim of broadening the scope of Janus-type polymers with new functionalities, Janus-type miktoarm star copolymers comprising helical poly(phenyl isocyanide) (PPI) and a vinyl polymer were designed and synthesized via a combination of Pd(II)-initiated isocyanide polymerization and atom transfer radical polymerization (ATRP). A functional β-cyclodextrin bearing 7 Pd(II) complexes at one side and 14 bromine groups at the other side ((Pd(II))7-CD-(Br)14) was prepared and used as an initiator for the one-pot polymerization of phenyl isocyanide and the ATRP of vinyl monomers in a living and controlled manner. A variety of Janus-type copolymers with different structures and tunable compositions were facilely obtained by using this method. Thus, Janus-type copolymers composed of helical PPIs and tetraphenylethylene-modified vinyl polymers exhibited a significant circularly polarized luminescence performance in both soluble and aggregated states. Meanwhile, Janus-type copolymers containing PPIs and hydrophilic vinyl polymers presented amphiphilicity and self-assembled into diverse morphologies.

A Perspective on the Simulation of Electronic Circular Dichroism and Circularly Polarized Luminescence Spectra in Chiral Solid Materials.

Chiral materials have shown tremendous potential for many technological applications, such as optoelectronics, sensing, magnetism, information technology, and imaging. Characterization of these materials is mostly based on chiroptical spectroscopies, such as electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). These experimental measurements would greatly benefit from theoretical simulations for interpretation of the spectra as well as predictions on new materials. While ECD and CPL simulations are well established for molecular systems, they are not for materials. In this Perspective, we describe the theoretical quantities necessary to simulate ECD and CPL spectra in oriented systems. Then, we discuss the approximate strategies currently used to perform these calculations, what computational machinery is already available to develop more general approaches, and some of the open challenges for the simulation of ECD and CPL spectra in solid materials. When methods that are as reliable and computationally efficient as those for molecules are developed, these simulations will provide invaluable insight and guidance for the rational design of optically active materials.

(Resonance) Raman optical activity among chiroptical spectroscopies: Quo vadis?

AbstractAlthough the potential of Raman Optical Activity (ROA) spectroscopy in the field of organic and inorganic materials research has been well demonstrated, its practical application is still limited. This work shows historical background, current state of the art and challenges of ROA spectroscopy facing scientists today. Expectations and development prospects for the coming years are also discussed. Efforts have already been made to improve but also to properly interpret the ROA signal when the ROA technique is combined with other spectroscopies (i.e., ROA/Electronic Circular Dichroism and ROA/Circularly Polarized Luminescence). The paper shows how to intensify the ROA effect to shorten the spectrum accumulation time, control possible artefacts and support the analysis of ROA spectra with actual and new theoretical approaches. However, the challenge is to increase the interest in this technique among the academic community, develop reliable protocols and adapt them for practical use. National and international research networks can significantly contribute to the growth of methodologies and standardization in areas in which the ROA has so far been little used. This paper presents a perspective vision for the future progress of ROA alongside other chiroptical methods.

Boosting Circularly Polarized Luminescence from Alkyl-Locked Axial Chirality Scaffold by Restriction of Molecular Motions.

Boosting the circularly polarized luminescence of small organic molecules has been a stubborn challenge because of weak structure rigidity and dynamic molecular motions. To investigate and eliminate these factors, here, we carried out the structure-property relationship studies on a newly-developed axial chiral scaffold of bidibenzo[b,d]furan. The molecular rigidity was finely tuned by gradually reducing the alkyl-chain length. The environmental factors were considered in solution, crystal, and polymer matrix at different temperatures. As a result, a significant amplification of the dissymmetry factor glum from 10-4 to 10-1 was achieved, corresponding to the situation from (R)-4C in solution to (R)-1C in polymer film at room temperature. A synergistic strategy of increasing the intramolecular rigidity and enhancing the intermolecular interaction to restrict the molecular motions was thus proposed to improve circularly polarized luminescence. The though-out demonstrated relationship will be of great importance for the development of high-performance small organic chiroptical systems in the future.

Chiral Multidentate Ligand Facilitating Perovskite Nanocrystals with Circularly Polarized Luminescence and Chiral Assembly

AbstractChiral ligand modification has emerged as a promising route to confer intrinsic chirality in perovskite nanocrystals (NCs), thereby imparting them with optically active properties and rendering great superiority in the next generation of circularly polarized luminescence. However, the functionalization of chiral ligand is not fully explored and the underlying mechanism governing chirality transfer remains elusive. Herein, tryptophan (Try), a naturally occurring chiral amino acid, is verified to serve as multidentate chiral ligands attaching on the surface of perovskite NCs. Such strong coordination favors the chirality imprinting on the electronic state of CsPbBr3, resulting in notable circular dichroism features and circularly polarized luminescence with a maximum glum of 2.3 × 10−3. It is intriguing that the intermolecular interaction between Try ligands anchored on two neighboring NCs contribute to chiral optical properties as well. The RDG‐NCI analysis have confirmed the hydrogen bond between the amine and carboxylic groups on chiral Try, which may drive the chiral assembly of perovskite NCs.

Controllable Circularly Polarized Luminescence with High Dissymmetry Factor via Co-Assembly of Achiral Dyes in Liquid Crystal Polymer Films.

Circularly polarized luminescence (CPL) materials are highly demanded due to their great potential in optoelectronic and chiroptical elements. However, the preparation of CPL films with high luminescence dissymmetry factors (glum ) remains a formidable task, which impedes their practical application in film-based devices. Herein, a facile strategy to prepare solid CPL film with a high glum through exogenous chiral induction and amplification of liquid crystal polymers is proposed. Amplification and reversion of the CPL appear when the films are annealed at the chiral nematic liquid crystalline temperature and the maximal glum up to 0.30 due to the enhancement of selective reflection. Thermal annealing treatment at different liquid crystalline states facilitates the formation of the chiral liquid phase and adjusts the circularly polarized emission. This work not only provides a straightforward and versatile platform to construct organic films capable of exhibiting strong circularly polarized emission but also is helpful in understanding the exact mechanism for the liquid crystal enhancement of CPL performance.

Light-Driven Sign Inversion of Circularly Polarized Luminescence Enabled by Dichroism Modulation in Cholesteric Liquid Crystals.

Stimuli-responsive circularly polarized luminescence (CPL) materials show great promise in applying information encryption and anticounterfeiting. Herein, light-driven CPL sign inversion is achieved by combining a photoresponsive achiral negative dichroic dye (KG) and a static achiral positive dichroic dye (NR) as dopants at the 0.5:0.5 weight ratio into the cholesteric liquid crystal (CLC) host. The side chains of KG undergo trans/cis isomerization after 365nm UV light irradiation, leading to the dichroism (SF) decrease. The |glum| value of CLC doping with KG (CLC-KG) weakens from 0.67 to 0.28 in response to the order degree change. Taking advantage of its unique CPL response property, the light-driven CPL sign inversion is achieved (from -0.20/0.14 to 0.02/-0.04) by incorporating NR (0.5:0.5) into the CLC-KG with helical superstructure static. Based on the synergistic use of circular polarization and responsiveness state as cryptographic primitives, the multidimensional information encryption CLC system can be realized.

Structurally Diverse Pyrene-decorated Planar Chiral [2,2]Paracyclophanes with Tunable Circularly Polarized Luminescence between Monomer and Excimer.

We reported the synthesis of a series of structurally diverse CPL-active molecules, in which pyrene units were installed to chiral pm/po-[2,2]PCP scaffolds either with or without a triple bond spacer for pm/po-PCP-P1 and pm/po-PCP-P2, respectively. The X-ray crystallographic analyses revealed that these pyrene-based [2,2]PCP derivatives exhibited diverse structures and crystal packings in the solid phases. The pyrene-based [2,2]PCP derivatives exhibit various (chir)optical properties in organic solutions, depending on their respective structures. In a mixture of dioxane and water, pm/po-PCP-P1 emit green excimer fluorescence, whereas pm/po-PCP-P2 emit blue one. The chiroptical investigation demonstrated that Rp-pm-PCP-P1 and Rp-pm-PCP-P2 exhibited completely opposite CD and CPL signals even they possess the same chiral Rp-[2,2]PCP core. The same argument also holds for other chiral pyrene-based [2,2]PCP derivatives. The theoretical calculation revealed that these unusual phenomena were attributed to different orientation between transition electric dipole moments and the magnetic dipole moments originating from the presence or absence of a triple bond spacer. These pyrene-based [2,2]PCP derivatives display various colours and fluorescence emissions in the solid state and PMMA films, possibly due to the different packings as observed in the crystal structure. Moreover, these compounds also can interact with perylene diimide through π-π interactions, leading to near-white fluorescence.

Helicity Control of Circularly Polarized Luminescence from Aromatic Conjugated Copolymers and Their Mixture Using Reversibly Photoinvertible Chiral Liquid Crystals.

We synthesized cyclic chiral compounds [(R)/(S)-D2s] by linking a photoresponsive bisbenzothienylethene (BTE) moiety with an axially chiral binaphthyl moiety. Chiral nematic liquid crystals (N*-LCs) were prepared by adding chiral compounds as dopants to host N-LCs. These N*-LCs exhibited reversible chirality inversion upon photoisomerization between the open and closed forms of the BTE moiety. Here, the mechanism underlying chirality inversion in photoresponsive N*-LCs was investigated by comparing the helical twisting powers (HTPs) of (R)-D2s with those of analogous compounds. It was found that the helical inversion of N*-LCs containing (R)-D2s is governed by a delicate balance between two types of opposite helicity, i.e., the right-handed helicity of the inherently chiral binaphthyl moiety and the left-handed helicity of the BTE moiety bearing intramolecularly induced chirality. Namely, (R)-D2s induced chirality of the BTE moiety, which is attributed to intramolecular chirality transfer from the axially chiral binaphthyl moiety to the BTE moiety. Thus, (R)-D2s are chiral compounds with double chirality consisting of an intrinsically chiral moiety and an intramolecularly induced chiral moiety. Photocontrol of the helical senses and reversible photoinversion of the N*-LCs are achieved by utilizing UV and visible light irradiation and the steric effects of the substituents at the binaphthyl rings in (R)-D2s. In addition, photocontrol of the induced circularly polarized luminescence (CPL) was achieved using the photoinvertible N*-LC. The achiral aromatic conjugated copolymers that exhibited red, green, and blue fluorescence were dissolved and mixed in the present N*-LC, and they exhibited left- and right-handed white CPL with large dissymmetry factors (|glum|) ranging from 0.2 to 1.0. The CPLs were reversibly photoswitched due to photoisomerization between the open and PSS forms of the chiral compounds through UV and visible light irradiation.

Polarized luminescence in single upconversion NaYbF4:Er rods

Rare earth-doped micro/nano-crystals are promising as microscopic fluorescent probes for monitoring local environment parameters, particularly for orientation tracking.

Combined performance of circularly polarized luminescence and proton conduction in homochiral cadmium(ii)–terbium(iii) complexes

A pair of Cd2Tb enantiomers shows coexsistence of CPL-active and proton conductive properties, offering a promising strategy for the development of multifunctional materials.