Synthesis, structure and luminescence properties of metal-organic frameworks based on benzo-bis(imidazole)

Metal-organic frameworks(MOFs)constructed from conjugated organic ligands are candidates for hybrid photoactive materials with potential applications.Compared to that from the ligands only,the intensity and wavelength of the luminescence could be tuned after they were incorporated in extended framework.In this report,by using an organic ligand with azolate moiety,benzo-bis(imidazole)(H2BBI),we synthesized two new MOF structures.Framework 1([Co(H2BBI)(DMSO)2Cl2]n,DMSO=dimethyl sulfoxide),constructed from tetrahedral Co(II)and H2BBI,exhibits zigzag 1D structure.Meanwhile,framework 2([Cu2(H2BBI)3(DMSO)6(NO3)4]n),a layered structure with hcb topology,was assembled from tetragonal pyramidal Cu(II)and H2BBI.Furthermore,2 exhibits strong luminescence emission(ex=280 nm).A blue shift of 40 nm(from 359 nm to 319 nm)was observed in framework 2 compared to the free ligand,which could be explained by the ligand-to-metal charge transfer in the network.     

Synthesis and luminescence properties of the europium quaternary complexes nanoparticles

In this paper,the nanometer-sized(200 nm)quaternary rare-earth complex Eu(BA)(TTA)2phen was successfully prepared by using the method of optimizing chemical precipitation.The characterizations of these nanoparticles were performed by using elemental analysis,thermogravimetric analysis,infrared spectroscopy,fluorescence spectroscopy,transmission electron microscopy and luminescence quantum-yield.The results indicate that they are better than common ternary complexes at light-emitting performance,luminescence properties,thermal stability,uniformity and particle size;they can also be further mixed with a suitable polymer to form functional rare earth polymers.Compared to the common solid materials,the quaternary complex has better and unique characteristics such as nanoparticle size effect and surface effect.A foundation had been laid for the further expansion of its application in the field of light-emitting and magnetic materials.     

Synthesis,Persistent Luminescence,and Thermoluminescence Properties of Yellow Sr3SiO5:Eu2+,RE3+ (RE=Ce,Nd, Dy,Ho, Er,Tm, Yb) and Orange‐Red Sr3−xBaxSiO5:Eu2+, Dy3+ Phosphor

Sunlight‐excitable orange or red persistent oxide phosphors with excellent performance are still in great need. Herein, an intense orange‐red Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ persistent luminescence phosphor was successfully developed by a two‐step design strategy. The XRD patterns, photoluminescence excitation and emission spectra, and the thermoluminescence spectra were investigated in detail. By adding non‐equivalent trivalent rare earth co‐dopants to introduce foreign trapping centers, the persistent luminescence performance of Eu²⁺ in Sr₃SiO₅ was significantly modified. The yellow persistent emission intensity of Eu²⁺ was greatly enhanced by a factor of 4.5 in Sr₃SiO₅:Eu²⁺,Nd³⁺ compared with the previously reported Sr₃SiO₅:Eu²⁺, Dy³⁺. Furthermore, Sr ions were replaced with equivalent Ba to give Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ phosphor, which shows yellow‐to‐orange‐red tunable persistent emissions from λ=570 to 591 nm as x is increased from 0 to 0.6. Additionally, the persistent emission intensity of Eu²⁺ is significantly improved by a factor of 2.7 in Sr_3?xBa_xSiO₅:Eu²⁺,Dy³⁺ (x=0.2) compared with Sr₃SiO₅:Eu²⁺,Dy³⁺. A possible mechanism for enhanced and tunable persistent luminescence behavior of Eu²⁺ in Sr_3?xBa_xSiO₅:Eu²⁺,RE³⁺ (RE=rare earth) is also proposed and discussed.     

Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2‐Acetylbenzo[b]thiophen‐3‐olate Ligand for Red Organic Light‐Emitting Devices

We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1 – 6 , which contain the 2‐acetylbenzo[b]thiophene‐3‐olate (bt) ligand, and their application in organic light‐emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10–20 % higher and lower emission self‐quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine‐tuned from orange (e.g., 2‐phenyl‐6‐(trifluoromethyl)benzo[d]thiazole (cf₃bta) for 4 ) to pure red (e.g., lpt (Hlpt=4‐methyl‐2‐(thiophen‐2‐yl)quinolone) for 6 ) by varying the cyclometalating ligands (C‐deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3‐bis(carbazol‐9‐yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A^?1, respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4‐(6H‐indolo[2,3‐b]quinoxalin‐6‐yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)₂Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)₂Ir(acac)]; 6 a in this work) [Adv. Mater.­ 2011 , 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3‐hydroxynaphtho[2,3‐b]thiophen‐2‐yl)(thiophen‐2‐yl)methanone) ligand, a substituted derivative of bt, the [(cf₃bta)₂Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film.     

A Luminescent Hypercrosslinked Conjugated Microporous Polymer for Efficient Removal and Detection of Mercury Ions

A hypercrosslinked conjugated microporous polymer (HCMP‐1) with a robustly efficient absorption and highly specific sensitivity to mercury ions (Hg²⁺) is synthesized in a one‐step Friedel–Crafts alkylation of cost‐effective 2,4,6‐trichloro‐1,3,5‐triazine and dibenzofuran in 1,2‐dichloroethane. HCMP‐1 has a moderate Brunauer–Emmett–Teller specific surface (432 m² g⁻¹), but it displays a high adsorption affinity (604 mg g⁻¹) and excellent trace efficiency for Hg²⁺. The π–π* electronic transition among the aromatic heterocyclic rings endows HCMP‐1 a strong fluorescent property and the fluorescence is obviously weakened after Hg²⁺ uptake, which makes the hypercrosslinked conjugated microporous polymer a promising fluorescent probe for Hg²⁺ detection, owning a super‐high sensitivity (detection limit 5 × 10⁻⁸ mol L⁻¹).

     

二维配位聚合物[Tb(1,4⁃bdc)1.5(phen)(H2O)]n的合成、晶体结构及对Fe3+离子的荧光检测

通过溶剂热反应成功合成出一种新型2D配位聚合物[Tb(1,4-bdc)_1.5(phen)(H₂O)]_n(1)(1,4-H₂bdc=对苯二甲酸;phen=菲咯啉)。对其进行了单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱表征。X射线衍射晶体学分析表明,配合物1结晶于三斜晶系P1空间群,2个相邻的Tb(Ⅲ)离子与4个1,4-bdc^2-通过—O—C—O—桥联成双核单元,并进一步通过1,4-bdc^2-桥联成二维层状结构。荧光实验证明配合物1可以通过荧光猝灭机制检测Fe₃₊,Ksv=8.39×10³ L·mol-1,检测限为0.017μmol·L^-1。     

高中有机化学教学中提升核心素养并体味科学价值*——以“乙炔的化学性质”为例

介绍了“乙炔的化学性质”的教学设计思路,展现了如何利用创新实验、丰富素材和问题讨论,帮助学生理解有机物性质和结构之间的关系。主要涉及以下几个环节:(1)通过课前自主预习,从乙炔与乙烯的相似性入手,预测乙炔的性质,了解乙炔的实验室制法;(2)结合2个创新分组实验“基于井穴板的微型化气体连续制备和性质检验装置”“利用真空输液瓶、微型样品瓶和注射器的密闭气体微型反应装置”,教师和学生一起巩固了乙炔的实验室制法,验证了预测的化学性质,丰富了对乙炔性质的感性认知,发现了“乙炔不能使酸性K₂Cr₂O₇溶液褪色”的异常现象;(3)从尝试解释异常现象入手,教师和学生一起从键能、加成比例、聚合后主链结构等多个角度探讨了乙炔与乙烯性质和结构的差异,建立起有机物官能团与性质关系的认知模型;(4)通过尝试利用模型解释2000年诺贝尔化学奖“导电高分子”和2017年度国家自然科学成果一等奖“AIE聚集诱导发光材料” 的结构、性质与应用,教师和学生一起提升了对认知模型的理解建构,感悟了科学研究的乐趣,体会化学科学在促进人类文明发展和社会进步中的重要作用。     

New Luminescent Lanthanide Tetrakis-Complexes NEt4[LnL4] Based on Dimethyl-N-Benzoylamidophosphate

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt₄[LnL₄] (Ln³⁺=La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt₄⁺ on the structure and properties of the tetrakis-complex [LnL4]^- is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of ⁵D₀→⁷F₄ transition, observed in the luminescence spectrum of NEt₄[EuL₄], is discussed based on theoretical calculations.     

Ternary zero-dimensional hybrid metal halides with dual emission

Bulk assemblies of zero-dimensional (0D) metal halides with ‘host-guest’ system provide a promising platform for rationally structural tunability and photoluminescence modulation. In this work, we first report a series of ternary 0D metal halides, (bmpy)₉[Pb₃Cl₁₁](MnCl₄)_2-2x(SbCl₅)_2x (bmpy⁺ = 1-buty-1-methylpyrrolidinium⁺, C₉NH₂₀⁺), where the organic cation bmpy⁺ cocrystallizes with [Pb₃Cl₁₁]^5- trimer clusters, [MnCl₄]^2? tetrahedra, and [SbCl₅]^2? pyramids. The emission color of (bmpy)₉[Pb₃Cl₁₁](MnCl₄)_2-2x(SbCl₅)_2x can be easily tuned from green to warm white and finally to orange-red by controlling the excitation wavelength or the [SbCl₅]^2?/[MnCl₄]^2? molar ratio, promising its potential for application in multicolor light-emitting devices or even in encrypting multilevel optical codes. This work presents a novel structural modulation strategy to fabricate superior ordered single-crystalline multicomponent materials with multifunctionalities of 0D luminescent metal halides.