Abstract Organic materials with switchable dual circularly polarized luminescence (CPL) are highly desired because they can not only directly radiate tunable circularly polarized light themselves but also induce CPL for guests by providing a chiral environment in self‐assembled structures or serving as the hosts for energy transfer systems. However, most organic molecules only exhibit single CPL and it remains challenging to develop organic molecules with dual CPL. Herein, novel through‐space conjugated chiral foldamers are constructed by attaching two biphenyl arms to the 9,10‐positions of phenanthrene, and switchable dual CPL with opposite signs at different emission wavelengths are successfully realized in the foldamers containing high‐polarizability substitutes (cyano, methylthiol and methylsulfonyl). The combined experimental and computational results demonstrate that the intramolecular through‐space conjugation has significant contributions to stabilizing the folded conformations. Upon photoexcitation in high‐polar solvents, strong interactions between the biphenyl arms substituted with cyano, methylthio or methylsulfonyl and the polar environment induce conformation transformation for the foldamers, resulting in two transformable secondary structures of opposite chirality, accounting for the dual CPL with opposite signs. These findings highlight the important influence of the secondary structures on the chiroptical property of the foldamers and pave a new avenue towards efficient and tunable dual CPL materials.
Yb(3+) and Er(3+) co-doped Gd2O3 nanoparticles were synthesized via a simple homogeneous precipitation method followed by subsequent heat treatment. Morphology characterization results showed that these nanoparticles were almost spherical in shape with diameters of 200-400 nm. The particles were further modified by polyethylene glycol (PEG) to improve their suspensibility in water. The sintering temperature was found to greatly influence the fluorescent properties of the products. After calcination at 700-1200 °C, the Gd2O3:Yb,Er nanoparticles could emit bright up-conversion fluorescence under 980 nm near-infrared (NIR) laser light excitation. The mechanism of up-conversion fluorescence was studied in detail and a three-photon process was observed for both green and red up-conversion fluorescence of the Gd2O3:Yb,Er nanoparticles. Different from many other Yb(3+),Er(3+) co-doped up-conversion materials, the prepared Gd2O3:Yb,Er nanoparticles emitted much stronger red light than green light. The reason was investigated and ascribed to the presence of abundant hydroxyl groups on the surface of the nanoparticles as a result of PEGylation. The nanoparticles could be taken up by the human cervical cancer (HeLa) cells and presented low toxicity. Well-selected photodynamic therapy (PDT) drugs, methylene blue (MB) with a UV/Vis absorption maximum (λmax) of 665 nm and 5-aminolevulinic acid (5ALA) which is a precursor of the natural photosensitizer photoporphyrin IX (PpIX) with a λmax of 635 nm, were loaded onto the nanoparticles respectively to obtain Gd2O3:Yb,Er-MB and Gd2O3:Yb,Er-5ALA nanoparticles. Being up-conversion nanoparticles (UCNPs), the taken up Gd2O3:Yb,Er nanoparticles exposed to 980 nm laser light emitted red fluorescence which activated the loaded MB and PpIX, and then killed the HeLa cells via a PDT mechanism. In vitro therapeutic investigation evidenced the prominent PDT effects of Gd2O3:Yb,Er-MB and Gd2O3:Yb,Er-5ALA upon NIR light irradiation. In magnetic resonance imaging (MRI) studies, the relaxivity values obtained for Gd2O3:Yb,Er were r1 = 2.2705 M(-1) s(-1) and r2 = 3.0675 M(-1) s(-1) with a r2/r1 ratio close to 1, suggesting that it would be a good candidate as a positive MRI agent. It is expected that these particles have applications in magnetic-fluorescent bimodal imaging and NIR light-triggered PDT.
Abstract Organic materials with switchable dual circularly polarized luminescence (CPL) are highly desired because they can not only directly radiate tunable circularly polarized light themselves but also induce CPL for guests by providing a chiral environment in self‐assembled structures or serving as the hosts for energy transfer systems. However, most organic molecules only exhibit single CPL and it remains challenging to develop organic molecules with dual CPL. Herein, novel through‐space conjugated chiral foldamers are constructed by attaching two biphenyl arms to the 9,10‐positions of phenanthrene, and switchable dual CPL with opposite signs at different emission wavelengths are successfully realized in the foldamers containing high‐polarizability substitutes (cyano, methylthiol and methylsulfonyl). The combined experimental and computational results demonstrate that the intramolecular through‐space conjugation has significant contributions to stabilizing the folded conformations. Upon photoexcitation in high‐polar solvents, strong interactions between the biphenyl arms substituted with cyano, methylthio or methylsulfonyl and the polar environment induce conformation transformation for the foldamers, resulting in two transformable secondary structures of opposite chirality, accounting for the dual CPL with opposite signs. These findings highlight the important influence of the secondary structures on the chiroptical property of the foldamers and pave a new avenue towards efficient and tunable dual CPL materials.
We demonstrate an effective strategy for brightness modulation via the surface charge treatment of electrodes. The brightness can be raised by 110% due to the growth of a colloidal lattice.
New deep-blue molecules compromised of tert -butyl modified anthracene, p -benzonitrile, and carbazole derivatives provide external quantum yields of 7.03% and 7.28% in non-doped and doped deep-blue OLEDs, respectively.
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