Enhanced Horizontal Dipole Orientation by Novel Penta-Helicene Anthracene-Based Host for Efficient Blue Fluorescent OLEDs.

Due to the relatively low photoluminescence quantum yield (PLQY) and horizontal dipole orientation of doped films, anthracene-based fluorescent organic light-emitting diodes (F-OLEDs) have faced a great challenge to achieve high external quantum efficiency (EQE). Herein, a novel approach is introduced by incorporating penta-helicene into anthracene, presented as linear-shaped 3-(4-(10-phenylanthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (BABH) and 3-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)dibenzo[c,g]phenanthrene (NABH). These blue hosts exhibit minimal intermolecular overlap of π-π stacking, effectively suppressing excimer formation, which facilitates the effective transfer of singlet energy to the fluorescent dopant for PLQY as high as 90%. Additionally, the as-obtained two hosts of BABH and NABH have effectively demonstrated major horizontal components transition dipole moments (TDM) and high thermal stability with glass transitional temperature (Tg) surpassing 188 °C, enhancing the horizontal dipole orientation of their doped films to be 89% and 93%, respectively. The OLEDs based on BABH and NABH exhibit excellent EQE of 10.5% and 12.4% at 462 nm and device lifetime up to 90% of the initial luminance over 4500 h at 100 cd m-2, which has firmly established them as among the most efficient blue F-OLEDs based on anthracene to date to the best knowledge. This work provides an instructive strategy to design an effective host for highly efficient and stable F-OLEDs.

Unique Surface Fluorescence Induced from the Core-Shell Structure of Gallium-Based Liquid Metals Prepared by Thermal Oxidation Processing.

Liquid metals (LMs) have emerged as promising functional materials that combine the properties of both liquid and metal. These characteristics enabled them to find applications in many fields. However, the LMs usually can only display a silver-white physical appearance, which limits their further applications in the fields with the imposition of stringent requirements for color and aesthetics. Herein, we report that the surface of LMs was transformed directly from metal to fluorescent semiconductor layer by an example of eutectic GaInSn (eGaInSn) induced by thermal oxidation. Specifically, a core-shell structure is formed from the fluorescent layer and the LMs. The shell endows the LMs with fluorescence without affecting their interior fluidity and conductivity. In particular, the formation process as well as the degree of crystallization, phase transformation, and light emission of the fluorescent oxide shell on the surface of LMs is regulated by the component content. A thorough analysis of surface morphology, composition, structure, and properties of the fluorescent shell suggests that the Ga2O3 layer is formed on the surface of gallium-based LMs after their immersion in deionized water. Subsequently, thermal oxidation results in the formation of the ß-Ga2O3 shell on the surface of liquid metals. Importantly, abundant oxygen vacancies (VO) in ß-Ga2O3 as the donors and the gallium vacancies (VGa), gallium-oxygen vacancy pairs (VO-VGa), defect energy levels, and intrinsic defects as the acceptors enabled the light emission. The fluorescent LMs have promising potential for flexible lighting and displays, anticounterfeiting measures, sensing, and chameleon robots.

Conjugated Polymers with Aggregation-Induced Emission Characteristics for Fluorescence Imaging and Photodynamic Therapy.

Accurate diagnosis and treatment have been extensively developed in the field of biomedicine, which put forward higher requirements for the development of biomedical materials with high efficiency and selectivity. Among them, conjugated polymers featuring aggregation-induced emission (AIE) characteristics (AIE conjugated polymers) have stood out in recent years owing to their unique properties, such as intense solid emission, high light-harvesting ability, efficient energy transfer, and high 1 O2 generation ability, which empower them with effective biomedical functions in fluorescence imaging (FLI), photodynamic therapy (PDT), FLI-guided PDT, two-photon excited photodynamic therapy (2PE-PDT), etc. In this review, we highlight recent progress in AIE conjugated polymers and their applications in anticancer and antibacterial areas based on FLI and PDT, and summarize the mechanism of color-tuned fluorescence emission and efficient 1 O2 generation ability. The challenges and perspectives for the future development of AIE conjugated polymers are also discussed.

Fluorescent linear polyurea based on toluene diisocyanate: Easy preparation, broad emission and potential applications.

In contrast to conventional fluorescent polymers featured by large conjugation structures, a new class of fluorescent polymers without above conjugations are gaining constant interest owing to their significant academic importance and promising applications in diverse fields. These unconventional fluorescent polymers are in general composed of heteroatoms (e.g. N, O, P, and S) under different forms. Here we report our recent study on polyurea, prepared by a very simple one step precipitation polymerization of toluene diisocyanate in a binary solvent of water-acetone. This polyurea, basically consisting of phenyl ring and urea group, shows fluorescent emission in a broad concentration range, from very low (10-5 mg/mL) to its solubility limit (50 mg/mL), and in a wide range of emission wavelength from UV to visible regions of up to 500 nm under varied excitation wavelength. The emission behaviors were fully studied under different concentrations and excitations. It was concluded that the emission in UV region was intrinsic due to the conjugation between the phenyl and the adjacent urea unit; while the emission in visible region, strongly excitation dependent, was caused by the cluster formation of the molecular chains, in accordance with the cluster-triggered-emission (CTE) mechanism. The formation of the cluster was tested through dynamic light scattering, FTIR and UV absorbance. Tested in presence of different metal ions, Fe3+ demonstrated a quenching effect with high selectivity. Based on this study, different paper-based sensors were designed to detect Fe3+, H2O2 in bioanalysis and for data encryption. This work provides a simple way to prepare a polyurea, a novel type of unconventional fluorescent polymer, with high emission performance distinct from its known analogues.

Influence of Group Modification at the Edges of Carbon Quantum Dots on Fluorescent Emission.

We present a detailed investigation on the effect of functional group modulation at the edges of carbon quantum dots (CQDs) on the fluorescence from the CQDs. The CQDs attached by N, S, and P elements are synthesized via pyrolysis of a mixture of citric acid and NH3H2O, H2SO4, and H3PO4, respectively. Thus, part of -COOH at the edges of CQDs can be converted into -C=O and functional groups such as -NH2, -SO2, -HSO3, and -H2PO4 can connect to the carbon bonds. We find that the formation of the N/S/P-CQDs can reduce the amount of -COOH that attaches to the edges of sp2-conjugated π-domains located at centers of these CQDs. This effect can result in the reduction of the non-radiative recombination for electronic transition in these CQDs. As a result, the quantum yield (QY) for fluorescence from the CQDs can be efficiently enhanced. We demonstrate experimentally that the QYs for N/S/P-CQDs can reach up to 18.7%, 29.7%, and 10.3%, respectively, in comparison to 9% for these without functional group modulation. This work can provide a practical experimental approach in improving the optical properties of fluorescent CQDs.

HS- facilitated sulfur pyran realizing hydrogen sulfide detection and imaging in HepG2 cells and chlorella.

The new carbazole-based fluorescent probe CA-1 was designed and synthesized for the high selective detection of H2S based on HS- facilitated sulfur pyran resulting in UV-Vis and fluorescent spectra changes. At the same time, the probe showed good sensitivity to the detection of H2S with a low detection limit of 0.16 µM. The detection process can be monitored by naked eye: with the addition of H2S, the probe system changed from yellow to pink. Importantly, the probe could be applied in monitoring H2S in HepG2 cells and Chlorella. These results indicate that CA-1 can be used as a promising fluorescent probe for the detection of H2S in situ.

Detection of Zn2+, Cd2+, Hg2+, and Pb2+ ions through label-free poly-L-glutamic acid.

Detection of heavy metal ions in water is important for environmental sustainability and food safety. Current fluorescent sensors interact with metal ions directly through chelation or chemical reactions. Those sensors are expensive to produce and often can detect only one ion at a time. Here we report a fluorescent turn-on sensor that can detect three group IIB metal ions and Pb2+ ions through label-free polypeptides in water. In our sensor-polypeptide mixture, Zn2+, Cd2+, Hg2+, and Pb2+ ions induce helix formation and inter-chain aggregation in poly-L-α-glutamic acid (PGA). The acridinium-based sensor molecules incorporate into the polypeptides and emit strongly with characteristic color for each group IIB ion under UV lamp. By adjusting the size of polypeptides or the length of the side chain carboxyl groups, we can selectively turn off or turn on the sensor emission for Hg2+ ions.

Synthesized Blue Fluorescent Protein Analogue with Tunable Colors from Excited-State Intramolecular Proton Transfer through an N-H···N Hydrogen Bond.

A synthesized blue fluorescent protein (BFP) chromophore analogue 2-BFP ((4Z)-4-[(1H-imidazol-2-yl)methylene]-1-methyl-2-phenyl-1H-imidazol-5(4H)-one) displays dual fluorescent emission that arises from the same Z-isomer. The larger Stokes shift emission is a result of excited-state intramolecular proton transfer (ESIPT) mediated by an N-H···N type of hydrogen bond. Compared to other green fluorescent protein (GFP) analogues with ESIPT such as o-HBDI, 2-BFP possesses greatly enhanced quantum yields and much slower proton-transfer rates. In addition, fluorescence up-conversion experiments revealed two rising components of lifetime for the tautomer formation of 2-BFP. The results imply that the relaxation of the N* state in 2-BFP triggers the proton transfer of the molecule. The weaker photoacidity of N-H is proposed to be crucial for these photophysical and photochemical properties. Finally, the ESIPT process in 2-BFP is inhibited in protic solvents (MeOH) or by the formation of metal-chelate complexes, providing insights for further developments and applications of ESIPT molecules.

Proton-Triggered Hypsochromic Luminescence in 1,1'-(2,5-Distyryl-1,4-phenylene) Dipiperidine.

A proton-triggered hypsochromic luminescent chromophore 1,1'-(2,5-distyryl-1,4-phenylene) dipiperidine (DPD) was designed and synthesized. Upon treatment by hydrochloric acid (HCl), the emission of DPD showed a large hypsochromic shift in both THF solution and microcrystals. Theoretical calculations and powder X-ray diffraction experiments reveal that the switchable emission of DPD originated from the change of the distribution and the spatial arrangement of the frontier molecular orbitals, and the different stacking modes of DPD in microcrystals also contribute to the switchable emission of DPD in aggregates.

Cu nanoclusters with aggregation induced emission enhancement.

A facile and versatile method for preparing water-soluble, stable, luminescent Cu nanoclusters (NCs) via the process of size-focusing etching from nonluminescent nanocrystals is presented. Using glutathione as a model ligand, the smallest cluster, Cu2 , is selectively synthesized to form a nearly monodisperse product, eliminating the need for tedious size fractionation. Evolution of photoluminescence and absorption spectra reveal that the formation of stable cluster species occurs through surface etching. Intriguingly, the as-prepared CuNCs exhibit an aggregation-induced emission enhancement effect. The CuNCs emit a faint light when dispersed in aqueous solution, but generate a striking fluorescence intensity enhancement upon aggregation. Armed with these attractive properties, the emissive CuNCs are expected to open new opportunities for the construction of light-emitting diodes, chemosensors, and bioimaging systems.