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.

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.

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.

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.

The improvement of photocatalysis O2 production over BiVO4 with amorphous FeOOH shell modification.

A novel amorphous FeOOH modified BiVO4 photocatalyst (A-FeOOH/BiVO4) was successfully produced and characterized by various techniques. The results showed that amorphous FeOOH with about 2 nm thickness evenly covered on BiVO4 surface, which caused resultant A-FeOOH/BiVO4 exhibiting higher visible light photocatalytic performance for producing O2 from water than BiVO4. When the covered amount of amorphous FeOOH was 8%, the resultant photocatalyst possessed the best photocatalytic performance. To find the reasons for the improvement of photocatalytic property, electrochemical experiments, DRS, PL and BET, were also measured, the experimental results indicated that interface effect between amorphous FeOOH and BiVO4 could conduce to migration of photogenerated charge, and exhibit stronger light responded capacity. These positive factors promoted A-FeOOH/BiVO4 presenting improved the photocatalytic performance. In a word, the combination of amorphous FeOOH with BiVO4 is an effective strategy to conquer important challenges in photocatalysis field.

Selective sensing and visualization of pesticides by ABW-type metal-organic framework based luminescent sensors.

A new ABW-type luminescent metal-organic framework (MOF) namely (H3O)[Zn2L(H2O)]·3NMP·6H2O (1), constructed with eco-friendly Zn2+ and the multicarboxylate intraligand (LH5) was designed, synthesized and fully characterized by X-ray single-crystal diffraction, steady-state absorption and emission spectroscopy, and SEM observations. The MOF-based suspension sensor 1 (NMP) demonstrated high sensitivity to low-concentration pesticides of chlorothalonil (CTL), nitrofen (NF), trifluralin (TFL), and 2,6-dichloro-4-nitroaniline (DCN), which was assigned to the synergistic effect of the photoinduced electron transfer and the fluorescence resonance energy transfer. With the highest luminescent detection efficiency (K SV up to 11.194 µmol-1 and LOD down to 2.93 ppm) to DCN, 1 (NMP) was successfully applied for the selective sensing of DCN. The MOF-based film sensor 1 (film) illustrated the selective visualization sensing of trace amounts of DCN. In addition, based on the high saturated vapor pressure of TFL and the unique bathochromic shift effect to the emission maxima of 1, the MOF-based luminescent vapor sensing device 1 (LED) successfully exhibited operability for sensing of TFL vapor. The results illustrated a feasible approach to construct new MOF-based luminescent sensors for selective sensing and visualization of pesticides.