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.

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.

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.

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 365 nm 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.

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 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.

Induced Red Circularly Polarized Luminescence Emission Promoted by Intermolecular Förster Resonance Energy Transfer through a Cholesteric Liquid Crystal Medium.

In this paper, planar chiral helicenes based on [2.2]paracyclophane PCPH5 acted as both chiral inducers and energy donors to construct the circularly polarized luminescence (CPL)-active ternary cholesteric liquid crystals (T-N*-LCs) in a commercial nematic liquid crystal (SLC1717, N-LCs) medium. Induced red CPL emission based on the energy acceptor of the achiral polymer DTBTF8 could be successfully promoted by the intermolecular Förster resonance energy transfer mechanism. The resulting T-N*-LCs can generate intensive CPL signals with glum up to +0.70/-0.67. Interestingly, this kind of "on-off" CPL switching of T-N*-LCs can be manipulated by the applied direct current electric field.

Induced CPL-Active Materials Based on Chiral Supramolecular Co-Assemblies.

Circularly polarized luminescence (CPL) has attracted much interest due to its potential applications on chiral photonic techniques and optoelectronic materials science. As known, dissymmetry factor (gem ) of CPL is one essential factor for evaluating the features of CPL-active materials. Much attention has focused on how to increase the gem value, which is one of the most important issues for CPL practical applications. Recently, more and more works have demonstrated that chiral supramolecular could provide the significant strategy to improve the gem value through the orderly helical superstructure of chiral building blocks. Normally, this kind of chiral supramolecular assembly process can be accompanied by chirality transfer and induction mechanism, which can promote the amplification effect on the induced CPL of achiral dyes. In this review, we fully summarized recent advances on the induced CPL-active materials of chiral supramolecular co-assemblies, their applications in circularly polarized organic light-emitting diodes (CP-OLEDs) and current challenges.

Remarkable White Circularly Polarized Electroluminescence Based on Chiral Co-assembled Helix Nanofiber Emitters.

White circularly polarized organic light-emitting diodes (CP-WOLEDs) are of great significance in potential lighting sources and full-color 3D displays. However, High-performance white CP-EL sources are almost unexplored. We have constructed full-color CP-EL devices based on chiral co-assemblies by using three achiral conjugated pyrene-based dyes (BP, w-WP and c-WP) doped with chiral binaphthyl-based enantiomers (S-/R-M) as the EMLs through an intermolecular chirality induction mechanism. (S-/R-M)0.2 -(c-WP)0.8 films exhibit regular helix nanofibers under annealing treatment and emit strong white CPL. Significantly, remarkable CP-WOLEDs based on (S-/R-M)0.2 -(c-WP)0.8 were achieved with |gEL | values as high as 6.2×10-2 and an excellent CRI of 98 at the CIE coordinates of (0.33, 0.33). These are the highest gEL and CRI values of reported CP-WOLEDs to date. This is the first achievement of CP-WOLEDs based on chiral co-assembled helix nanofiber emitters, and provides a valuable strategy with which to develop white CP-EL for future practical applications.

Inverted and Amplified CP-EL Behavior Promoted by AIE-Active Chiral Co-Assembled Helical Nanofibers.

It is well-known that high-performance circularly polarized organic light-emitting diodes (CP-OLEDs) remain a formidable challenge to the future application of circularly polarized luminescent (CPL)-active materials. Herein, the design of a pair of AIE-active chiral enantiomers (L/D-HP) is described to construct chiral co-assemblies with an achiral naphthalimide dye (NTi). The resulting co-assemblies emit an inverted CPL signal compared with that from the L/D-HP enantiomers. After thermal annealing at 120 °C, the inverted CPL signal of this kind of L/D-HP-NTi with a 1:1 molar ratio shows regular and ordered helical nanofibers arranged through intermolecularly ordered layered packing and is accompanied with a further amplified effect (|gem | = 0.032, λem  = 535 nm). Significantly, non-doped CP-OLEDs based on a device emitting layer (EML) of L/D-HP-NTi exhibits a low turn-on voltage (Von ) of 4.7 V, a high maximum brightness (Lmax ) of 2001 cd m-2 , and moderate maximum external quantum efficiency (EQEmax ) of 2.3%, as well as excellent circularly polarized electroluminescence (CP-EL) (|gEL | = 0.023, λem  = 533 nm).

Dynamically stable and amplified circularly polarized excimer emission regulated by solvation of chiral co-assembly process.

Chiral supramolecular assembly has been assigned to be one of the most favorable strategies for the development of excellent circularly polarized luminescent (CPL)-active materials. Herein, we report our study of an achiral boron-containing pyrene (Py)-based chromophore (PyBO) as a circularly polarized excimer emission (CPEE) dye induced by chiral co-assemblies containing chiral binaphthyl-based enantiomers (R/S-M). Chiral co-assembly R/S-M-(PyBO)4 fresh film spin-coated from toluene solution can exhibit orderly nanofibers and strong green CPEE (λem = 512 nm, gem = ±0.45, ΦFL = 51.2 %) resulting from an achiral PyBO excimer. In contrast, only a very weak blue CPL was observed (λem = 461 nm, gem = ± 0.0125, ΦFL = 19.0 %) after 187 h due to PyBO monomer emission as spherulite growth. Interestingly, this kind of chiral co-assembly R-M-(PyBO)4-T film from tetrahydrofuran (THF) solution retains uniform morphology and affords the most stable and strongest CPEE performance (λem = 512 nm, gem = + 0.62, ΦFL = 53.3 %) after 10 days.

Dynamic Circularly Polarized Luminescence with Tunable Handedness and Intensity Enabled by Achiral Dichroic Dyes in Cholesteric Liquid Crystal Medium.

Cholesteric liquid crystals (CLCs) are chiral supramolecular systems that self-assemble into a highly regular helical arrangement in a liquid crystal (LC) medium. Such an arrangement is highly beneficial for the chiral enlargement effect on circularly polarized luminescence (CPL) signals. Dichroic dyes with rod-like molecular structures can exhibit fluorescence anisotropy along both the long and short molecular axes owing to their transition dipole moment (TDM) vectors. In this work, a pair of donor-accepter (D-A) achiral dichroic dyes is prepared, namely, 3,4-ethylenedioxythiophene derivative (P1, whose TDM vector is parallel to the long axis of the molecule, i.e., F||  > F⊥ ) and anthraquinone derivative (N1, whose TDM vector is perpendicular to the long axis of the molecule, i.e., F||  < F⊥ ). CLCs can be fabricated by doping P1 or N1 together with chiral 1,1'-binaphthyl-derived inducers into SLC1717 medium. Dynamic CPL with tunable handedness and intensity is achieved by changing the N1:P1 mass ratio, and the luminescence dissymmetry factor (gem ) value reaches |0.71|. This work describes the first observation of dynamic CPL with tunable handedness and intensity enabled by TDM regulation of achiral dichroic dyes in a CLC medium.

Amplified Circularly Polarized Electroluminescence Behavior Triggered by Helical Nanofibers from Chiral Co-assembly Polymers.

Two chiral binaphthyl polymers (R/S-P1 and R/S-P2) with different dihedral angles of the binaphthyl moiety were chosen as chiral inducers to construct chiral co-assemblies with an achiral pyrene-naphthalimide dye (NPy) and then acted as the emitting layer (EML) of circularly polarized electroluminescence (CP-EL) devices. The anchored dihedral angle of R/S-P2 not only exhibited the enhanced chirality signal, but also had a strong chirality-inducing effect on the achiral NPy dye in the chiral co-assembly (R/S-P2)0.6 -(NPy)0.4 . After annealing at 120 °C, the CPL signal (|gem |) of ordered helical nano-fibers (R/S-P2)0.6 -(NPy)0.4 was amplified to 5.6×10-2 , which was about 6-fold larger than that of (R/S-P1)0.6 -(NPy)0.4 . The amplified gem value of (R/S-P2)0.6 -(NPy)0.4 was due to the formation of a helical co-assembly through the strong π-π stacking interaction between the R/S-P2 and the achiral NPy. This kind of ordered helical nano-fibers (R/S-P2)0.6 -(NPy)0.4 acted as the EML of CP-OLEDs, and achieved an excellent CP-EL performance (|gEL |=4.8×10-2 ).

Inverted Circularly Polarized Luminescence Behavior Induced by Helical Nanofibers through Chiral Co-Assembly from Achiral Liquid Crystal Polymers and Chiral Inducers.

Chiral supramolecular assembly can provide a powerful strategy for developing circularly polarized luminescence (CPL)-active materials by forming helices or superhelices into single or multiple components. Herein, we chose three achiral liquid crystal polymers (LC-P1/P2/P3) and chiral binaphthyl-based inducers (R/S-M) with anchored dihedral angles to construct chiral co-assemblies and explore the induced CPL behavior from pyrenyl (Py) emitters in achiral LC polymers through the regulation of helical nanofibers during the supramolecular co-assembly process. Most interestingly, chiral co-assembly (R/S-M)0.1-(P3)0.9 emitted an inverted blue-colored CPL signal during thermal annealing treatment at the glass transition temperature due to the flexible main chain of the LC polymer (LC-P3). The strongest blue-colored CPL emission for the (R/S-M)0.1-(P3)0.9 spin-coated film (λem = 455 nm, |gem| = 6.47 × 10-2, ΦF = 48.5%) could be detected by using thermal annealing treatment at 105 °C.

Strong CPL-active liquid crystal materials induced by intermolecular hydrogen-bonding interaction and a chirality induction mechanism.

A novel co-assembly material can emit strong CPL signals (λem = 485 nm, glum = +0.076/-0.064) from an achiral AIE-active ß-cyanostilbene (CYS) liquid crystal dye through intermolecular hydrogen bond (HB) interaction and chirality induction after a rapid cooling quench treatment.

Controllable Circularly Polarized Electroluminescence Performance Improved by the Dihedral Angle of Chiral-Bridged Binaphthyl-Type Dopant Inducers.

Chirality of 1,1'-binaphthol (BINOL) is due to the restricted rotation between two naphthalene rings, and its skeletal structure of binaphthyl unit can be further modified by choosing functionalized substituents to afford the enlarged chiral induction effect. In this paper, we designed and synthesized nine chiral binaphthyl derivatives (R/S-1-R/S-9) as circularly polarized electroluminescence (CP-EL) inducers by inserting various bridged alkyl chains into the hydroxyl groups of BINOL or introducing functionalized substituents with different steric hindrances on the 3,3'-position of 2,2'-methylenedioxy-1,1'-binaphthalene. Their molecular conformations and CPL behaviors of nine chiral inducers were significantly dependent on the length of the alkyl chain and the degree of substituent steric hindrance, which could further regulate their chiral induction effect on achiral fluorescent polymer F8BT from small to large in the doped films. Moreover, in virtue of the planar rigid conjugated molecular conformation of R/S-1, R/S-6, and R/S-9, the amplified CPL signals (|gPL|) were detected as high as 2.36 × 10-2, 2.06 × 10-2, and 1.26 × 10-2 from blends of F8BT and these chiral inducers. The circularly polarized organic light-emitting diode (CP-OLED) device on the blends of F8BT and chiral inducers (R/S-6) with small dihedron angle and excellent carrier mobility showed a low turn-on voltage (Von < 4.5 V), high brightness (> 10509.6 cd/m2), and maximum |gEL| value of 1.86 × 10-2 (F8BT + 5% R/S-6). This work can develop and provide a valuable reference for CP-OLED device design through chiral dopant induction.

Deep Blue Circularly Polarized Luminescence Response Behavior of an Achiral Pyrene-Based Emitter Regulated by Chiral Co-assembly Helical Nanofibers.

Supramolecular co-assembly provides a brand-new powerful strategy for regulating simple organic molecules into various hierarchical nano- and microstructures as smart functional materials. In particular, chiral supramolecular assemblies with strong fluorescent emission have received extensive attention for their application as circularly polarized luminescence (CPL) emitters. Herein, we synthesized three achiral pyrene derivatives, but only the chiral co-assembly (R/S-NMe2-Py-2) can exhibit the regular and orderly helical nanofiber via π-π stacking interaction between chiral N,N'-dimethyl-binaphthyldiamine enantiomers (R/S-NMe2) and the achiral pyrene derivative (Py-2). Interestingly, this kind of 2:1 molar ratio (R/S-NMe2)2-Py-2 co-assembly with a helical nanofiber structure can emit a strong deep blue CPL signal from the achiral pyrene-based emitter, and the dissymmetry factor gem value can reach 0.027 (λem = 423 nm) in the film from spin-coating.

Ultrasensitive Nucleic Acid Assay Based on Cyclometalated Iridium(III) Complex with High Electrochemiluminescence Efficiency.

This work developed a sensitive electrochemiluminescence (ECL) biosensor based on a cyclometalated iridium(III) complex ((bt)2Irbza), which was synthesized for the first time. Annihilation, reductive-oxidative, and oxidative-reductive ECL behaviors of (bt)2Irbza were investigated, respectively. The oxidative-reductive ECL intensity was the strongest compared with the other two, which showed 16.7 times relative ECL efficiency compared with commercial [Ru(bpy)3]2+ under the same experimental conditions. Therefore, an ECL biosensing system with (bt)2Irbza as the anodic luminophore was established for miRNA detection based on a closed bipolar electrode (BPE). Combined with both steric hindrance and catalytic effects induced by hemin/G-quadruplex in the cathodic reservoir of BPE that changed the Faraday current of the cathode and thus mediated the ECL intensity of (bt)2Irbza in the anode of BPE, the ECL sensor stated an ultrahigh sensitivity for microRNA (miRNA-122) analysis with a detection limit of 82 aM.

Ultrastrong Red Circularly Polarized Luminescence Promoted from Chiral Transfer and Intermolecular Förster Resonance Energy Transfer in Ternary Chiral Emissive Nematic Liquid Crystals.

Chiral emissive liquid crystals (N*-LCs) have been proved to greatly amplify the circularly polarized luminescence (CPL) signals due to highly regular spiral arrangement of dyes in a well-organized liquid crystals system. Normally, CPL materials with a high luminescence dissymmetry factor (glum) and quantum yield (QY) can meet the real application requirement. Here, four chiral aggregate-induced emission (AIE) active donors (Guests A1-A4: R-C2, R-C4, R-C6, R-C8, chiral dopant, and energy donor) and achiral AIE-active acceptors (Guest B: PBCy, CPL emitter) were doped into the commercial nematic liquid crystals E7 (N-LCs, Host) to form CPL-active ternary chiral emissive N-LCs (T-N*-LCs), respectively. This kind of T-N*-LCs could emit strong red CPL with QY = 16.56% and glum up to 1.51 through intermolecular energy transfer and chirality induction from the supramolecular self-assembly of T-N*-LCs. This work provides the effective strategy for the development of high glum CPL materials.

Solution-Processed White Circularly Polarized Organic Light-Emitting Diodes Based on Chiral Binaphthyl Emitters.

By combining the blue and orange CPL or functionalized bis-benzoxanethones emitters (S-/R-BN-tCz and S-/R-BN-PXZ), warm white CP-OLEDs were fabricated using solution-processed single emitting layer strategy. The successful realization of white CP-EL benefited from the same stable binaphthyl chirality and similar rigid structure of the two emissive CPL emitters. The devices exhibited the low turn-on voltage of ≈4.3 V, maximum luminance of ≈10200 cd m-2 and maximum current efficiency of ≈2.0 cd A-1 . Most significantly, the devices with CIE coordinates of (0.32, 0.45) displayed intense CP-EL signals in the spectral range of 450 to 650 nm, and showed stable gEL values of ≈10-3 as the luminance increased from 100 to 6000 cd m-2 . To the best of our knowledge, this work provides for the first time a simple and feasible strategy to fabricate solution-processed white CP-OLEDs based on the co-doping of the CPL emitters.

Strong-Induced CPL Emission Promoted from Achiral Conjugated Polymer-Containing Emissive Nematic Liquid Crystals (P-N*-LCs).

With the rapid development on 3D printing technology, more and more works have been devoted to 3D display. 3D display will really come true by using circularly polarized luminescence (CPL)-active materials with both high quantum yield and dissymmetry factor (gem ) in organic light-emitting diode or liquid crystals (LCs). But so far most of these CPL materials cannot meet the real application requirement because of the low gem values in the range of 10-5 -10-2 . In this paper, ternary chiral emissive LCs (P-N*-LCs) is designed by doping chiral binaphthyl-based enantiomers as chiral dopant (Guest 1) and achiral conjugated polymer as induced CPL emitter (Guest 2) into nematic liquid crystal (N-LCs) Host 5CB. Both Guest 1 and Guest 2 show excellent compatibility with Host 5CB. The obtained ternary P-N*-LCs can emit strong-induced CPL signal with gem up to 1.12 and ФFL up to 66.1%. This work first develops a new strategy for the smart design of excellent CPL materials from versatile achiral conjugation fluorescence polymers.