Absolute control of helicity at the C-termini in quinoline oligoamide foldamers by chiral oxazolylaniline moieties

Absolute one-handed chiral quinoline tetramers andoctamers containing different oxazolylanilines at the C-terminus have been synthesized.The absolute one-handed sense and diastereomeric excess values were valued by^1H NMR.X-ray crystal diffractionand CD studies reveal that the S-oxazolylaniline always induces a P-handed helicity and the absolute helicity is driven by the stable three-center hydrogen bonding between protons in the amide and N atoms in oxazolylaniline and adjacent quinoline ring.CPL investigations demonstrated that S-CQn-a-d are CPL active and its g(lum)values are dependent on its length.Interestingly,the sizes of the substituents in the chiral centers are different,howeve r,they exert no effect on the dissymmetric factors g(abs)and g(lum)of quinoline oligoamide foldamers.     

Shedding Light on the Origin of Solid-State Luminescence Enhancement in Butterfly Molecules

Different molecular strategies have been carefully evaluated to produce solid-state luminescence enhancement (SLE) in compounds that show dark states in solution. A set of α-phenylstyrylarene derivatives with a butterfly shape have been designed and synthesised, for the first time, with the aim of improving the solid-state fluorescence emission of their parent styrylarene compounds. Although these butterfly molecules are not fluorescent in solution, one of them (1,2,4,5-tetra(α-phenylstyryl)benzene) exhibits a fluorescence quantum yield as high as 68 % in a drop-cast sample and 31 % in its crystalline form. In contrast, 1,3,5-tris(α-phenylstyryl)benzene and 4,6-bis(α-phenylstyryl)pyrimidine do not show SLE. A range of fluorescence spectroscopy experiments and DFT calculations were carried out to unravel the origin of different photophysical behaviour of these compounds in the solid state. The results indicate that a rational strategy to control the SLE effect in luminogens depends on a delicate balance between molecular properties and inter-/intramolecular interactions in the solid state.     

白色荧光粉CaF2∶Yb3+/Eu3+/La3+的制备及其上转换发光特性

采用改进的两步高温固相熔融法制备了Yb^3+、Eu^3+、La^3+共掺杂CaF 2的上转换荧光粉。基于荧光猝灭原理,通过改变La^3+掺杂浓度来调节CaF 2∶Yb^3+/Eu^3+材料的发光性能,并在980 nm近红外光激发下,获得了该材料的白色上转换发光(UCL)。在该发光体系中,Yb^3+不仅起到了敏化Eu^3+的作用,同时,Yb^3+二聚体(Yb^3+-dimer)自身合作发出波长范围480~540 nm的绿色荧光。而白光三基色中的绿光正是来自Yb^3+二聚体的合作发光。Eu^3+则作为激活剂,同时发出红色和蓝色荧光。荧光寿命测试结果表明Yb^3+-dimer与Eu^3+之间存在有效的能量传递。值得注意的是,在980 nm激光激发下,1%La^3+掺杂的样品表现出最佳的红、绿、蓝三基色光比列,实现了材料的上转换白光发射,其色度坐标为(0.311,0.340)。     

Mechanochromic Delayed Fluorescence Switching in Propeller-Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli-Responsive Intramolecular Charge-Transfer Excited States

Herein, the universal design of high-efficiency stimuli-responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli-triggered TADF switching for a series of carbazole–isophthalonitrile-based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X-ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited-state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light-emitting diodes using a single TADF emitter.     

An Activatable Lanthanide Luminescent Probe for Time‐Gated Detection of Nitroreductase in Live Bacteria

Herein we report the development of a turn‐on lanthanide luminescent probe for time‐gated detection of nitroreductases (NTRs) in live bacteria. The probe is activated through NTR‐induced formation of the sensitizing carbostyril antenna and resulting energy transfer to the lanthanide center. This novel NTR‐responsive trigger is virtually non‐fluorescent in its inactivated form and features a large signal increase upon activation. We show that the probe is capable of selectively sensing NTR in lysates as well as in live bacteria of the ESKAPE family which are clinically highly relevant multiresistant pathogens responsible for the majority of hospital infections. The results suggest that our probe could be used to develop diagnostic tools for bacterial infections.     

Fe3+、Ce3+共掺杂γ-LiAlO2的发光性质

采用不同于传统固相反应法的制备方法合成了Fe,Ce 共掺杂γ-LiAlO₂。通过XRD和 SEM分析表明,采用这种方法能够成功获得尺寸小于10 μm的四方相结构γ-LiAlO₂荧光粉。从γ-LiAlO₂ ∶ Fe,Ce 的激发和发射光谱可以看出,通过引入少量的铈离子,我们首先发现了铈离子掺杂对样品的发光效率有明显的影响。并且随着铈离子浓度的增加,其发光效率也出现规律性的变化,而且发射光谱在Ce离子摩尔分数达到1.5%的情况下发光效率最强,当Ce离子摩尔分数达到3％时,发光效率明显下降。这种高效的荧光粉作为转光剂应用于人工植物照明和农用转光膜具有积极的意义。     

NaYF4∶Eu3+, Tm3+, Yb3+材料中Stokes和反Stokes发光研究

合成了Eu3+,Tm3+和Yb3+掺杂的NaYF₄材料。360 nm光激发呈蓝色发光,峰值位于452 nm,对应Tm3+的1D₂→3F₄跃迁;395 nm光激发呈橙色发光,峰值位于591 nm,对应Eu3+的5D₀→7F₁跃迁;409 nm光激发呈红色发光,峰值位于613 nm,对应Eu3+的5D₀→7F₂跃迁;980 nm光激发呈蓝色和红色发光,发光峰位于474和646 nm。蓝光来源Tm3+的1G₄ →3H₆跃迁,红光来源Tm3+的1G₄→3F₄跃迁。在双对数曲线中,蓝光474 nm和红光646 nm的斜率分别为2.1和2.4,在980 nm光激发下,蓝光和红光发射都是双光子过程。还研究了材料的吸收光谱,并利用X射线衍射,扫描电镜测试了材料的物相结构和微观形貌。结果表明：NaYF₄∶Eu3+, Tm3+, Yb3+材料具有较规则的六方相结构,结晶良好。     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

Preparation, Luminescence Properties, and Application of Scintillators Based on Lu3Al5O12:Ce Single‐Crystal Films

The possibility of obtaining scintillators with a high effective atomic number of the element Z _ef based on Lu₃Al₅O₁₂:Ce³⁺ singlecrystal films (SCF) on doping with La³⁺ and Sc³⁺ ions on Y₃Al₅O₁₂ substrates has been investigated. It is established that the SCF of (LuLaY)₃Al₅O₁₂:Ce³⁺ (Z _ef = 58.9 and = 6.67 g/cm²) does not rank below those of Y₃Al₅O₁₂:Ce³⁺ (Z _ef = 29 and = 4.52 g/cm²) in the conversion efficiency of radiation at the band with _max = 515 nm. This allows their use as screens of xray images with a space resolution of 0.75–1.00 m. It is suggested that in the SCF of Lu₃Al₅O₁₂ the isoelectronic impurities of lanthanum and scandium form radiative recombination centers of the type La_Lu, Sc_Lu, and ScAl as well as the centers Lu as a consequence of the effect of replacement of some Lu³⁺ ions by the La³⁺ ions to octanodes of the garnet lattice. The low efficiency of Ce³⁺ radiation in the SCF of (LuSc)₃(AlSc)₅O₁₂:Ce is explained by substantial losses due to excitation of the recombination luminescence in the UV region of the centers formed by the isoelectronic impurities of scandium and to the possible existence of the channel of energy excitation dissipation related to the transitions between extrema of the allowed energy bands and activator levels.     

反向驱动的异质结有机薄膜电致发光

成功制备了结构为ITO／PDDOPV／PPQ／Al的异质结聚合物发光二极管。该器件在正反向偏压下均可发光。在正向偏压下的光发射主要来自PDDOPV，但在反向偏压下的光发射则包括来自PPQ的蓝光发射和PDDOPV的黄光发射。蓝光强度与黄光强度的比值随着反向偏压的增加而增加，当反向直流电压分别为22V、24V、26V、28V时，其电致发光光谱中PPQ与PDDOPV的峰高比IPPQ／IPDDOPV分别为1．092、1．329、1．605、2．046。换句话说，该器件的发光颜色是压控可调的，这对实现彩色显示是极为有利的。分析了在反向偏压下的发光机理以及IPPQ／IPDDOPV受电压控制的原因。